S- Heterocycle-Based Monomers and Their High-Performance Materials

Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ytei of Synthesis il-hm il-n.D.e.a.Mra agrteUtras MSc Unterlass, Margarethe Miriam Dr.rer.nat. Dipl.-Ing. Dipl.-Chem. ooesadterhigh-performance their and Monomers hstei a are u ne h uevso fAssatProf. Assistant of supervision the under out carried was thesis This dacdOgncMtrasRsac Group Research Materials Organic Advanced arc atrFritz Walter Patrick ono ac 17 March on born nttt fMtrasChemistry Materials of Institute arclto ubr01325048 number matriculation ehiceUiesttWien Universität Technische ete 6 80Rankweil 6830 16, Reitweg N- atrThesis Master coe 6 2019 16, October Materials ina Austria Vienna, & umte by submitted S- th 93i Bregenz in 1993 , heterocycle-based BSc , Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. a ere oeecs oto noedmnin hr r oye hmss h hi ules u in but . . builders. chain the chemists, polymer wasteland” synthetic are There a it’s dimension. dimensions, one three in or control two exercise to learned has “ Organic hmssaemsefla xriigcnrli eodmnin.Oesbutr fogncchemists organic of subculture One dimensions. zero in control exercising at masterful are chemists I oadHoffmann Roland Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. oi ovnsadctlss hra S sasletfe ehd T tlzsol ae sasolvent. a to as heating water upon only utilizes water HTS of avoid method, properties solvent-free to changing a methods the is PIs, suitable utilizes SSP For are Whereas HTS materials product. (SSP), these catalysts. harmful of and polymerization environmentally solvents processing solid-state overall toxic in an and as in (HTP) well resulting polymerization as required, hydrothermal are synthesis, catalysts in and both solvents However, toxic (OPVs)). photovoltaics organic or ec,tihohnswr eindt etr uebetipeesse hl locnann moieties containing also while system thiophene SSP. assess tuneable enable solubility. to a of should tested feature degree that were some to strategies retain designed should of were product variety the trithiophenes a while Hence, SSP, problem, for this systems thiophene-based address To of processability suitability lack low. the usually rather polymers is these solubility However, their reported. because are procedure. precursors/polymers alternative such an of as examples few conducted was salts characterization monomer the prepared elim- complicating of is monomers, tetra(4-aminophenyl)methane, SSP anline HTP, used choice, conditions Besides of the hydrothermal significantly. precursor under as that amine well found, the as also from concentration), was inated It and significantly. time, polymerization reaction the (temperature, affect conditions the that shows materials. functional highly towards polymerization friendly environmentally their and as main precursors such the procedure. solvent of a non-toxic one of ubiquitous, are characteristics an solvents green using As the procedure, increases crystallinity. a greatly their of water enhances "greenness" as the well evaluating as when PIs, contributors of synthesis the enables which xdto,wihealste ob sdi lcrncdvcs( devices electronic in used be to them enables which oxidation, n ehnclsaiiy ec,te a eue o plctos hc eur aeil owithstand to materials require which applications, for used be can thermal ( chemical, they conditions (PTs) high extreme Hence, polythiophenes featuring and (HPPs) (PIs) stability. polymers polyimides high-performance mechanical Both are and tasks. PIs of polymers. plethora functional a highly fulfill are to tuned be can polymers Organic Abstract h eodpr drse h rprto fsldsaeplmrzbetipeepeusr sol a only as precursors thiophene polymerizable solid-state of preparation the addressed part second The work This (COFs). frameworks organic covalent thiophene-based 3D and PI-based synthesize amine- to both was part of first the synthesis of and goal The development the with deals thesis diploma This e.g. sisltr neetoi eie) T,o h te ad eoecnutv upon conductive become hand, other the on PTs, devices). electronic in insulators as III e.g. T 100 > rai ih-mtigdoe (OLEDs) diodes light-emitting organic ◦ C nacnndrato vessel, reaction confined a in Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. yeewreentwickelt. wurde Syteme u.U iss rbeez nesce udnvrcidn taeinvrog,wlh oolein Thiophen- SSP-fähige sowohl zwei Trithiophen welche an Ein gebunden verfolgt, Thiophen-Kern sollten. funktionalisierbaren Strategien gewährleisten einem Polymers verschiedene aus Löslichkeit des bestehend geringe wurden Löslichkeit System, geeignete sehr untersuchen auch eine zu als nur Monomer Probleme entsprechend oft SSP-fähiges diesese sich Polymere welche Um entsprechenden bekannt, die Monomere auf. weisen wenige Zudem nur sind lassen. Arbeit polymerisieren dieser Zeitpunkt Zum -Monomeren. alternative als SSP Be- auch herangezogen. wurde Monomersalzen hydrothermalen HTP von unter Neben Polymerisation zur dass erschwert. Methode signifikant gezeigt, Charakterisierung abgespalten die zudem (Tetra(4-aminophenylmethan)) was Ausgangsstoff wurde kann, verwendeten werden Es vom Anilin-Gruppe haben. eine Polymerisation dingungen die Wahl Ein- die auf welchen sowie Monomere untersucht Konzentration) und Arbeit der Reaktionszeit Diese (Temperatur, Reaktionsbedingungen frameworks). verwendeten organic die covalent fluss engl. vom (COFs Gerüstverbindungen auseinander. Materialien hochfunktionellen ubiquitäres, zu erhalten. ein Polymerisation zu an umweltfreundlicher Verfahren sich umweltfreundlicheres einer es ein Umweltfreundlichkeit bietet um der haben, nutzen zu Beurteilung Einfluss Wasser großen der wie einen bei Lösemittel Lösemittel Da ungiftiges Prozesses eines ermöglichen. zu bzw. PIs Synthese von Kristallisation die sowie ärn e T asrasenie öeitlvredtwr.DbintthdohraeSynthese hydrothermale nutzt Dabei 100 über Temperaturen wird. bei Wasser verwendet von Eigenschaften Lösemittel verändernden einziges Methode, sich lösemittelfreie die als eine (HTS) Wasser ist SSP Poly- HTP von vermeiden. bei Fall zu Lösemittel im während giftige stellen um polymerization) dar, solid-state Alternativen attraktive engl. imiden Polymerisation vom Hydrothermale (SSP Festphasenpolymerisation werden. Polymere und zurückgegriffen dieser Verarbeitung Katalysatoren (HTP) die und auch Lösemittel als Solarzellen Synthese organische organische die giftige für oder auf sowohl (OLEDs) Allgemeinen Ver- im Leuchtdioden zur muss organische Allerdings daher sich (z.B. (OPVs)). eignen für Bauteilen und Poly- sie elektronischen werden gemacht können werden. in leitfähig verwendet Daher wendung elektrisch Leiterplatten) Oxidation auf auszeichnen. durch Isolatoren können Stabilität (PTs) als thiophene thermische (z.B. und Bedingungen extremen chemische unter hohe Eigen- Anwendungen mechanischen ihre ihre ausze- durch durch Flexibilität besonders sowie ihre sich welche schaften, durch Hochleistungspolymere, besonders sind sich (PIs) welche Polyimide dar, ichnet. Materialklasse eine stellen Polymere Organische Kurzfassung e wieTi isrAbi ecätg ihmtdrSnhs o ethsnoyeiirae Thiophen festphasenpolymerisierbaren von Synthese der mit sich beschäftigt Arbeit dieser Teil zweite Der organischen kristallinen, PI-basierten von Synthese die war Arbeit dieser Teils ersten deren des und Ziel Monomeren thiophenbasierten Das und amin- von Synthese der mit sich setzt Diplomarbeit Diese IV ◦ C u mdeSynthese die um aus , Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. h teswoedrdm uigdffiuttmsadmd ytm nVen repleasure. true a all Vienna and in Stefan time Simon, my Nick, made Michael, and times Eleonora, difficult pleasure. Barbara, me during true keeping Andreas, me a for Alwin, endured years you friends who 2 Thank dear others last years. my the these 2 making thank last for to the and during want my breaks support I and take her home grandparents to for at Teresa my me spent girlfriend thank forcing moment my to sane, single thank like to every also want making would also for I I and today. calls but am phone financially I me many person supporting special. throughout the for me Walter, be supporting and to Andrea for me parents, sisters raising my course for the to throughout owed all me is of helped gratitute have most who highest university, My the of life. outside my people of the all thank to want furthermore I att hn tfnWbrwomd tpsil o et s hi H their use to me for possible it made conducted. who he Weber and measurements Stefan expertise SCXRD thank invaluable the to His for want analytics. Stöger I X-ray Berthold of to area owed the is me. in Gratitude impress help his to Miriam, for failed Artner never group. Werner kindness incredible thank Z., an to Miriam want such Olivier, also experienced you! L., I Thank Lukas have solved, - Marianne, to be Simon Musthafa, to greateful supported and Elias, had have forever Eleonora problem Marwan, which am or Hipassia, of had, Fabián, I I All Michael, and question Tobia, would group. me what Alonso, I matter Unterlass for No conferences. the there during in thesis. were this had friends they of and we stages colleagues time various and other great the lab throughout my the Musthafa the me all and Mohamed in thank and COFs weeks Lahnsteiner to on first Marianne like discussions my thank also delightful to during want many me I on the friend. eye for allowed and an Iqbal and partner keeping significantly lab for excellent grow design an Bumbaris to being to Elias me for me thank throughout helped allowed to me it even want as helped and furthermore picture. opportunity, ideas who I bigger this own Unterlass, the my value M. see with especially to Miriam up I me come Prof. own. to my supervisor me on pushed my projects always thank Miriam to thesis. like whole would my I point this At Acknowledgements V 2 uolv setup. autoclave Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. “ o ypreswohv upre etruhu yetr live” entire my throughout me supported have who partens my For VII Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. eea Background General 2 Polyimides I Introduction 1 Acknowledgements Kurzfassung Abstract Contents eut n Discussion and Results 4 Motivation and Aims 3 . yrtemlSnhss...... 13 ...... 12 ...... 8 ...... 7 ...... 4 ...... Synthesis . . Hydrothermal ...... 2.6 ...... Synthesis . COF . . in . . . Methods . Synthetic ...... 2.5 ...... Linkages . . Dynamical . . . . 2.4 ...... Structures . COF . 2.3 Chemistry Reticular 2.2 C 2.1 . IbsdFrameworks PI-based 4.1 .. AMudrH odtos...... 18 . 17 ...... 18 ...... Conditions . HT . under . . TAPM Precursors . as TrisAPM . 4.1.3 and . TAPM . TAPM 4.1.2 of Preparation 4.1.1 .. ae ne yrtemlCniin 14 . 12 13 . . 12 ...... 12 ...... 12 11 ...... 11 ...... 10 ...... 10 ...... 8 ...... 7 ...... Conditions . . . . Hydrothermal ...... under ...... Water ...... Polyimides . . . . of ...... Synthesis 2.6.2 ...... Hydrothermal ...... 2.6.1 ...... Synthesis ...... Mechanochemical ...... Synthesis 2.5.4 ...... Microwave ...... Synthesis 2.5.3 ...... Ionothermal ...... Synthesis 2.5.2 ...... Solvothermal ...... 2.5.1 ...... Linkages . . . . . C-C ...... Linkages 2.4.4 . . . Imide ...... Linkages 2.4.3 . C-N ...... Linkages 2.4.2 B-O ...... 2.4.1 . . . . . Topologies 3D . . Topologies 2.3.2 2D 2.3.1 vln rai rmwrs...... 4 ...... Frameworks Organic ovalent via yrtemlPlmrzto 17 ...... Polymerization Hydrothermal IX 16 17 IV III 3 V 4 1 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. eut n Discussion and Results 7 Motivation and Aims 6 eea Background General 5 Polythiophenes II Conclusion 8 . nta et ...... Tests Initial 7.1 . oyhohns...... 47 . . . . 46 . . 48 ...... Poly(3,4-ethylenedioxythiophene) ...... 5.3 . Polythiophenes . . 5.2 Polymers Conductive 5.1 . raie nCF n aeil cec 37 ...... Science Materials and COFs in Triazines 4.2 . ocuinadOtok...... 57 ...... 53 ...... Outlook and . Conclusion . . 7.3 ...... Systems DBEDOT Functionalized of Preparation 7.2 .. ocuinadOtok...... 44 ...... 43 . . . . 37 ...... 39 ...... 40 ...... 39 ...... 36 ...... 41 . 37 ...... Outlook . . . . . and ...... Conclusion Derivatives . . . . its . . . and ...... BATB Systems 4.2.8 . of . Aminal-linked . . . . Crystallography towards . 31 . . . . . Derivatives . . and . . . . BATB . . 4.2.7 . . . of . . . Polymerization ...... BATB-COFs . . Imine-based 28 . . . . of . . . 4.2.6 . . . Synthesis Conventional . Derivatives . . . . . and 35 . . . . . BATB . of ...... 4.2.5 Polymerization . . . Attempted . . . Precursor 24 DATz ...... 33 Versatile . . . A . . . 4.2.4 - ...... BATB ...... Precursors . . . . . COF . . 4.2.3 . as ...... 2,4-Diamino-1,3,5-triazines ...... Art . . . . . the . 26 4.2.2 . . of . . . . State ...... 4.2.1 ...... 28 ...... Outlook . . . . . and ...... Conclusion 21 . . 20 TrisAPM:MellA . . . . of 4.1.16 . . . . Characterization . . . . . and . . . . . Polymerization . . . . TrisAPM:PMDA . . . . of . 4.1.15 . . . . . 19 Characterization . . . and . . . . . Polymerization ...... Micrographs . 4.1.14 . . . SEM . Salt . . . . . of Monomer . . Evaluation TAPM:PMA . . . . the ...... of 4.1.13 . 20 . Characterization . . . . and . . . Polymerization ...... 4.1.12 . . . . Salt . . . . Monomer . . . . TAPM:PMA . . . COFs . . TAPM:PMA . 4.1.11 . . . . Simulated . . with . . . Comparison . . Yield . . Reaction . . 4.1.10 . of . . . Evaluation . . TAPM:PMA . of . Characterization . Synthesis 4.1.9 . Framework and . Polymerization on . Species . TrisAPM-Cation . . the . 4.1.8 of . Implications . . Synthesis . HT 4.1.7 from Temperature TrisAPM-Carbocation and Time Reaction 4.1.6 of Evaluation 4.1.5 P 4.1.4 .. vlaigteEeto usiuin...... 55 . . . . . 52 ...... 52 . . . . 50 . 55 ...... Moieties . . EDOT . . Terminal . . Featuring . . Tri-thiophenes . . . of . . . Preparation . Substitution . . of . . Effect . 7.2.3 . the . . Evaluating ...... 7.2.2 ...... 7.2.1 . . . . . Results . Initial . the . . of Evaluation . . . . . 7.1.3 Polymerization . Hydrothermal . 7.1.2 Polymerization Solid-State 7.1.1 Wudl’s lmrzto n hrceiaino AMPD 18 ...... TAPM:PMDA of Characterization and olymerization rcdr piiigCniin 53 ...... Conditions Optimizing – Procedure X 50 . 45 49 46 58 50 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. Crystallization C Polyimides B Structures of List A xeietlPart Experimental 9 . oyhohns...... 80 ...... Polythiophenes 9.4 . oymds...... Polyimides 9.2 9.1 . imntizns...... 69 ...... Diaminotriazines 9.3 .. hmcl 80 . . . 86 ...... 84 . . . 77 . . . . . 80 ...... 75 ...... Systems . . . Trithiophene . . . of . . . Perparation . . . . systems . . . . 2-Substituted-EDOT . 9.4.4 of . . . Preparation PEDOT . . . and . BEDOT . . DBEDOT, . 9.4.3 of . . Preparation ...... 9.4.2 . . Chemicals . . . . 9.4.1 . . . . . DATz’s of . Polymerizations . Dimorpholinotriazines of 9.3.4 Synthesis 9.3.3 .. hmcl 69 ...... 61 . 61 ...... 64 ...... diaminotriazines . . . . of . . . Synthesis . General ...... 9.3.2 . Chemicals ...... 9.3.1 . Polymers . Organic . based . . TAPM– . of . Synthesis . . . TAPM . of 9.2.3 Synthesis . . . 9.2.2 Chemicals 9.2.1 eea ehd 60 ...... Methods General XI via yltieiain...... 69 ...... cyclotrimerization 61 . 104 92 88 60 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ito brvain n symbols and abbreviations of List eHmtao Vultraviolet triazine UV tris-(4-aminophenyl)methane diffraction X-ray TrisAPM tetraphenylmethane Tz XRD TPM tetra-(4-nitrophenyl)methane TNPM tetrahydrofurane THF framework analysis metal-organic thermographimetric methanol acid MOF TGA mellitic Kagomé MeOH dual Kagomé MellA hexatopic hexagonal kgm synthesis hydrothermal kdg polymerization hydrothermal hxl HTS HTP P ihpromneplmrTP tetra-(4-aminophenyl)methane TAPM hydrothermal polymer high-performance HT HPP c honeycomb hcb tHehnlSMsann lcrnmicroscopy electron scanning SEM sulfonate styrene poly polymerization solid-state polymer organic polythiophene porous PSS effect SSP heteroatom dianhydride pyromellitic POP diffraction X-ray single-crystal PT spectroscopy gaschromatography-mass PMDA SC-XRD poly-3,4-ethylenedioxythiophene HAE PEDOT GCMS ethanol polyimide trithiophene EDOT-thiophene-EDOT FT-IR EtOH 3,4-Eehylenedioxythiophene dimethylformamid ETE acid PI bond pyromellitic covalent dynamic EDOT 2,5-Dibromothiophene DMF PMA DCB DBT 2,5-Dibromo-3,4-ethyldioxythiophene 5,5’-Dibromo-2,2’-bithiophene DBEDOT diaminotriazine DBBT DATz cHaei cdNMP acid acetic AcOH O oaetogncdaeokpetn freaction of extent p resonance magnetic nucleus photovoltaics organic diode light-emitting organic dramework triazine NMR covalent OPV reactor steel dramework non-stirred organic OLED covalent center data NSTR crystallography CTF cambridge COF 2-Bromo-3,4-ethyldioxythiophene CCDC 2,4-Bisamino-1,3,5-triazine-benzene reflectance total attenuated BEDOT BATB ATR Ac 3MBDT 2 ctcahdieNBS anhydride acetic O ,-irm--ehlhohn muto substance of amount n 2,5-Dibromo-3-methylthiophene Fourier rnfrainifae q qaelattice square sql infrared transformation XII T t T p d eopsto temperature decomposition time temperature pressure N N -bromosuccinimide -methylpyrrolidone Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ito Figures of List .1Daioraie 38 . . 39 . 38 ...... 37 ...... 34 ...... 35 ...... 32 ...... 33 . . 30 ...... 28 . . . . . 31 ...... 27 ...... 23 24 ...... Polymer ...... 25 Theoretical ...... and ...... 22 DATz ...... 4.22 ...... Diaminotriazines ...... 4.21 ...... Triazines ...... of ...... Synthesis ...... 4.20 ...... CTFs ...... of ...... Applications ...... 4.19 ...... Structure . 26 ...... Theoretical . . . TrisAPM:MellA ...... 21 . . . 4.18 ...... XRD . . . TrisAPM:PMDA ...... Structure . . . 4.17 . . . Framework . 17 ...... Theoretical ...... and . . . TrisAPM . . . . . Polymerizates . 19 . . . . 18 . 4.16 hour ...... 120 . . . Polymerizations . . . . . of . . . Short . . . SEM ...... and . . . . . 4.15 MonSalt . . . . 20 . . . . the . . . SSPs ...... of . . its . . . SEM ...... and ...... 4.14 15 MonSalt ...... the ...... 14 . of ...... XRD ...... 4.13 . . . . NMR ...... Salt ...... Monomer ...... TAPM:PMA ...... 4.12 ...... Simulation ...... XRD ...... TAPM:PMA . . . . . TrisAPM-carbocation ...... 4.11 the ...... Incorporating ...... COF ...... Hypothetical Conc.-Screen ...... - . . 4.10 . . . . . XRD ...... TAPM:PMA ...... XRD . . 4.9 . . . . 2:5 ...... TAPM:PMA ...... 4.8 . . . IR ...... TAPM:PMA ...... 4.7 . . . . XRD . . . . TAPM:PMA ...... Implications . . . . . its . 4.6 . . . . and . TrisAPM-carbocation . TrisAPM-cation . . . the . . . and . . . . . Dyes . 4.5 . . Violet . . . . Crystal . . . . PMDA . . with . . . TAPM . 4.4 . . . of . Polymerization . . . TrisAPM . . and . . . TAPM . 4.3 . . of . Structure ...... TAPM . 4.2 . of . . Preparation ...... 4.1 ...... Water High-Temperature . Polarity 2.13 on . Effect . - HTW . 2.12 . Dye Perinone 2.11 . hs iga fWtr...... 13 . . . . 13 . . 11 ...... 8 ...... 7 ...... 6 ...... Synthesis ...... PI . . . . Zeolites Hydrothermal . . . . . of . . 2.10 . . Synthesis . . . . . Hydrothermal ...... Water . . . . of . . . 2.9 . . Diagram . . . Phase ...... Pathways . . . 2.8 . . Formation . . . Imide ...... 2.7 . . COFs . . Imine ...... 2.6 . . Linkers . COF . . . . . Topologies 2.5 . COF . 3D . . . Topologies 2.4 COF . 2D . 2.3 Chemistry Reticular 2.2 2.1 is O ytee 5 ...... Syntheses COF First via h ooe atRue...... 14 ...... Route Salt Monomer the XIII 14 10 9 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. . ytei fPDT...... 49 . . 48 ...... 48 ...... 47 ...... 46 . . . 47 ...... Polythiophenes . . . Functionalized . . . . . of . . . Synthesis ...... PEDOT . . . 6.2 . of . . . Synthesis ...... 6.1 ...... EDOT . . . of . . . . Synthesis ...... Polythiophenes . 5.5 of . . . Doping . . . . . 5.4 . Polythiophenes . 3-Substituted . . . Synthesis 5.3 Polythiophene . Conventional Polymers Conductive 5.2 of Examples 5.1 .4CytlSrcue n irgah fBT n 4-NO and BATB of Micrographs and Structures Crystal 4.24 4.23 .2BT ytei 69 . . . . . 69 ...... 68 . 66 . . . 65 . . . . 67 . . . . 64 . 63 ...... 65 ...... 62 ...... 64 ...... 61 ...... NO ...... of ...... Synthesis . . . . 55 ...... 9.13 ...... Synthesis ...... BATB ...... 56 . 9.12 ...... synthesis ...... DATz . . . . . General ...... 54 . . . . 9.11 . TrisAPM:MelA ...... of ...... Polymerization ...... Hydrothermal . TrisAPM:PMDA ...... of 9.10 . . . . . Polymerization ...... Hydrothermal ...... MonSalts ...... of 51 9.9 ...... Polymerization . . 52 . Solid-State ...... MonSalt . . . TAPM:PMA ...... 56 50 . . . the . . 9.8 ...... of . . . . . Synthesis ...... TrisAPM-carbocation ...... the . 53 . . 9.7 ...... of ...... Synthesis ...... 9.6 ...... Polymerization . . . . TAPM:PMA ...... 9.5 ...... Polymerization . . . . . TAPM:PMDA ...... TNPM . . . 9.4 . . . . of ...... Synthesis ...... TNPM . . . . . 9.3 . of ...... Synthesis ...... TPM . . . . 9.2 . of ...... Synthesis ...... 9.1 Thiophenes . . . . Functionalized . . . Terminally . . . . EDOT . . . . . of . . . . . Preparation ...... EDOT . . . . Substituted . . 7.8 . . of . . . . Preparation ...... BEDOT . . 7.7 . of . . . . Synthesis ...... DBEDOT 7.6 DBEDOT . of . . of Polmerization . SSP . . the . . . for 7.5 . Mechanism . SSP Proposed . Post . and . . Pre 7.4 . NMR . DBBT . DBBT of . HTP 7.3 . and SSP . . 7.2 . Dibromothiophenes 7.1 .4Snhsso NH of Synthesis 9.14 .0Snhsso 4-NH of Synthesis 9.20 .8Snhsso AQ...... 73 . . . 73 ...... 72 ...... 71 ...... 4-NO . . . . of Synthesis . . . . . 9.19 . . . DAAQ . . . of . Synthesis . . 9.18 . . 4PyrPhTz . . of Synthesis . . 9.17 . . 4COHPhTz . of Synthesis . 9.16 . 4COOHPhTz of Synthesis 9.15 .5SPo BDT...... 81 . . 81 . . . 80 ...... 79 . . 77 78 ...... A . . . Method . . . . BEDOT . . . of . . . Synthesis . . . . . 9.26 . . . . . DBEDOT . of . . . SSP . . . . 9.25 . . . . DBEDOT of . . . Synthesis . . 9.24 polymers . . Aminal-linked of . . Synthesis . . 9.23 . synthesis polyimine . Attempted . 9.22 DATz’s of Polymerization 9.21 mnllne oyes...... 42 ...... Polymers Aminal-linked 2 2 hz...... 70 ...... PhTz hz...... 71 ...... PhTz 2 2 hT 75 ...... PhMTz hT 76 ...... PhMTz XIV via S 49 ...... SSP 2 hT 43 ...... PhMTz Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. .3TAo AB...... 101 ...... 100 . . . . 102 . . . . 98 ...... 99 . . . 97 ...... 96 ...... 93 ...... 93 . 95 ...... 94 ...... 92 ...... BATB . . . . . of ...... TGA . . . . . systems . . . . . B.13 . DATz ...... of . . . . . measurements 87 ...... UV/VIS ...... B.12 ...... TrisAPM:MellA . . . . of ...... TGA ...... B.11 ...... TrisAPM:MellA screen . . . . . of . conc...... PXRD . . - . . . . . TrisAPM:PMDA B.10 . . . . . of ...... TGA ...... TriAPM:PMDA B.9 . . . . of ...... TGA ...... TrisAPM:PMDA . . B.8 . . of . . . . salt . . PXRD 82 . monomer . . . . . TAPM:PMA . . . the . B.7 . B of . . . 84 . . . salt IR . monomer . . . . . TAPM:PMA . . . . the B.6 . . A 86 . of . . . . salt . TGA . monomer . . . . . TAPM:PMA . . . . . the B.5 . . . of ...... TGA ...... B . . . . TAPM:PMDA B.4 . . of ...... IR . . . . . A . . . TAPM:PMDA B.3 . . of . . . . . IR . . . . . 85 . . TAPM:PMDA B.2 . . 84 of . . . 84 . TGA ...... B.1 ...... ETE . . . . . terthiophene . . the . . . . . of . . . . Bromination . A . . . . Method 9.34 . . 2,5-di(3,4-ethylenedioxythienyl)thiophene . . . . of . . . . Synthesis . B . . . Method 9.33 . . 2-Bromo-5-(aminophenyl)-3,4-ethylenedioxythiophene . . . of . . Synthesis . A . . Method 9.32 . 2-Bromo-5-(nitrophenyl)-3,4-ethylenedioxythiophene . . . of . . Synthesis . . . 9.31 . 2-Bromo-5-(chlorothienyl)-3,4-ethylenedioxythiophene . . of . Synthesis . 9.30 thiophenes 2-substituted . of Preparation C 9.29 Method BEDOT of Synthesis 9.28 9.27 ytei fBDTMto 82 ...... B Method BEDOT of Synthesis XV 103 . . Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ito Tables of List . IR 4.1 . AMPAMnmrSl G 29 ...... 41 ...... 40 ...... DATz . of . Polymerization . . Conventional Imides Towards the . DATzs in of . Used Polymerization Conditions . Conventional the . in 4.4 . Used Conditions . TGA Salt 4.3 Monomer TAPM:PMA 4.2 oe ...... modes XVI 23 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. T focus main the 19 and been the react have in materials they chemistry new organic how synthesizing of behave, for days findings molecules early these how the use during Understanding to how and centuries. compounds two new last form the in ( methods advancement pathways. and use human reaction means new desired new developing their finding and with fit known concerned using to is by it chemistry materials organic produce breaking/altering Hence, to by approach graphene). material top-down obtain a a to taking graphite creating of instead on materials focusses and molecules that building around revolves chemistry Organic Introduction 1 Chapter eur as odtosi hi ytee.Pliie Ps eogt hscaso Psadaeotnused often are and HPPs of catalysts class this on metal to stability, materials belong precious thermal (PIs) insulating or Polyimides and as chemical synthesis syntheses. solvents high their the harmful in as Secondly, conditions such environmentally harsh properties, of require uneconomic. high-performance employed use featuring are often polymers the blends are Especially requires such they [6]. often of as materials, recycling polymers cost. single-use a and these at as separation of come classified and has be humanity blends can of polymer prosperity polymers the as these hence, of and majority diversity a this However, Firstly, life. modern weight of part in crucial lighter being mass- while were durability, diamine, and a with strength fibers. small acid higher plant-based dicarboxylic from showed conventional a built than fibers polymers of war, derived are polycondensation world the the Hermann second polymers on because the organic based During 1922. produced, polymer that [5]. in a bonds realized, established Nylon, covalent as only by prize, such linked was Nobel are linked and a are monomers awarded so-called they molecules, later how was and formed who materials Staudinger, such how of standing fnwmtras hnlhhli 3,anwsadr Hidctr swl sa nutilyapplicable industrially achievements. an his of as examples well few as a indicator, only synthesis pH are the standard [4], in now indigo compounds towards a organic route of [3], petroleum-derived synthetic one Phenolphthalein using was of materials. Baeyer potential new von new untapped which of Adolf the at discover pace discovered. the to were accelerated first polymers molecules the useful organic of especially plethora and a obtain pharmaceuticals to materials, petroleum use to how from of molecule discovery organic field. an obtain the to of chemist pioneers first the the were [2], precursor, Wöhler inorganic Friedrich an or structure, chemical of theory the 300 > yrtemlplmrzto HP,atcnqeta ssecuieywtra ovn n solid-state and solvent a as water exclusively uses that technique a (HTP), polymerization Hydrothermal odt,apehr fogncplmr alrdt hi eie s aebe eeoe n r a are and developed been have use desired their to tailored polymers organic of plethora a date, To rai hmsr n seilyogncmtrasceitymgtb mns h ao ol enabling tools major the amongst be might chemistry materials organic especially and chemistry Organic vntog h rtogncplmr eedsoee uigteery20 early the during discovered were polymers organic first the though Even 19 late the In ◦ C n oi ovns( solvents toxic and th etr n seilywt h einn fte20 the of beginning the with especially and century e.g. e.g. ici ors oee,cnetoa ytei fsc aeil requires materials such of synthesis conventional However, boards. circuit M rNP,a ela aayt ( catalysts as well as NMP), or DMF th 1 etr.Ceit uha eué[] h developed who [1], Kekulé as such Chemists century. th e.g. etr,ti ou hne.The changed. focus this century, isoquinoline). th etr,adee under- deeper a century, e.g. scotch-taping Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. cvnigrsucsadms-rdcn e eie ofi uaiysneshsldt nenvironmental an to led CO has as needs such humanity’s gases fit Especially to devices crisis. new mass-producing and resources scavenging without materials high-performance [7]. produce solvents to toxic methods for known need only the the amongst are (SSP) polymerization prahsuighbi-aeil n vnflyogncsseshv endvlpd nieyorganic Entirely processability, facile developed. their been to have alternative due Hence, systems interest of organic energy. are fully of (PVs) How- amount even photovoltaics green silicon. immense and of on an hybrid-materials of based requires production using examples systems silicon the approaches photovoltaic few single-crystalline in using a of produced lies production only usually question the However, is essential ever, power Another Solar task. this energy. [8]. renewable tackle reported and high to been featuring materials have polymers promising syntheses network most eco-friendly crystalline the (COFs), candidates amongst frameworks potential in are organic are interest Covalent nature porosity, gained metal-organic air problem. even exhaust this and from inorganic solving gases organic, for of these materials separate Porous and years. capture recent can that materials developing Hence, eiain ohprsfauea nrdcint h oi htsol rvd h eesr background necessary the provide should that poly- conclusions. topic solid-state formulating the and for to results suitable introduction the monomers discussing an thiophene-based before feature of parts development Both the on merization. focusses polymerization part their second and monomers The of characterization and friendly COFs. synthesis the PI-based environmentally with towards deals using thesis materials the of functional part first highly SSP. The and synthesize HTS synthesis to as the was such employed. during work methods be However, this to have for polythiophenes. conditions motivation as harmful The materials, photovoltaics such Organic these polymers of systems. organic processing conventional on and to based compared generally time short are relatively (OPVs) in PVs large-area of duction nrcn er,i eaeaprn htorsceyi teigtwrsatpigpit eae of Decades point. tipping a towards steering is society our that apparent became it years, recent In 2 rmtaeaeaogttemjrdiigfre tciaechange. climate at forces driving major the amongst are methane or e.g. pncaig hc lostepro- the allows which spin-coating, HPE .INTRODUCTION 1. CHAPTER 2 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. Polyimides atI Part 3 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. edn oteatadsineo oa ytei,teetoshv o,utlrcnl,be xeddt the to extended been recently, until not, 2005, have In tools structures. these molecules 3D synthesis, elaborate and total increasingly 2D of synthesizing organic of science of humankind synthesis and task to the art known mastered the were has to to structures chemistry leading 3D way organic or rational though 2D a Even extended in extensive, crystalline, [9]. more structures fully-organic, were their COFs occuring synthesizing up naturally in by challenges open no their initial as to challenged the than solids, units, synthesis is extended building porous in chemistry and of crystalline challenges MOF make metrics different the Whereas vastly controlling show and (MOFs). COFs synthesizing frameworks bonds. metal-organic covalent counterpart by semi-organic together held Si) O, N, C Frameworks Organic Covalent 2.1 Background General 2 Chapter 1] ngnrl eiua ytei a eboe onit v tp Fg 2.2). (Fig. steps order five long-range into and down periodicity broken with be materials can organic chemistry synthesis extended reticular reticular other systems, a no organic general, For are In there MOFs. topology, [12]. and as specific COFs COFs a of to synthesis featuring unique the structures is in extended importance utmost of of synthesis is designed which the describes chemistry Reticular Chemistry Reticular 2.2 of is [9][11]. chemistry full accordingly COF for controlled that allow be indicates to to This system has the down correction. which in slowed error manner remain be enabling dynamic to to hence has highly has formation formation water bond challenges of secondly, the reaction two and the of crystallization, general, Firstly, reversibility proper In COFs. for such allow 2.1). of to synthesis enough the (Fig. ester in boronate frameworks overcome and be boroxine/boronate boroxine to porous reversible have the highly on in based resulted frameworks, These formation, [10]. COF-5 and COF-1 frameworks vln rai rmwrs(Os r xeddcytliesld,md flgteeet ( elements light of made solids, crystalline extended are (COFs) frameworks organic ovalent Yaghi 4 n ookr eotdtefis xeddorganic extended first the reported coworkers and e.g. ,B C, B, H, Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. eutn nbrnt esters. boronate in resulting acid iue2.1: Figure (1) A eutn nbrxn linkages. boroxine in resulting is O ytee:Snhtcshm o O- I n O- (II). COF-5 and (I) COF-1 for scheme Synthetic Syntheses: COF First O O B B O O B B O O B B (I) COF-1 O O B B B(OH) B(OH) O O (1) B B O O B B 2 2 B) O O B B hw h odnaino benzenediboronicacid of condensation the shows O O B B O O B B B O O B O O B O O B B O O O HPE .GNRLBACKGROUND GENERAL 2. CHAPTER O B(OH) B(OH) O 1 (2) (1) B O A) B hw h efcnesto fbenzenedibrononic of self-condensation the shows 2 2 O B B O O O (II) COF-5 O O B B (1) O O ihhexahydroxytriphenylene with O O O B O B HO HO B O O B OH OH O O O O B B O O O O O OH OH B O B (2) 5 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. oooy O-6abrnt-se ae n niiebsdCFwr hsnt hwhwdffrn ervln rcroscnlead can precursors tetravalent different – how Chemistry” show Reticular to to chosen “Introduction were from COF Adaptation based imine topologies. an different and vastly based to boronate-ester a COF-66 topology. 2.2: Figure Step 5:Characterization Step 4:Synthesis Step 3:Identifyingmolecularbuilding-blocks Step 2:Breaking atthehighestgeometry Step 1:Choosingatopology (HO) (HO) eiua hmsr:Gnrlptwyue nrtclrceityt eemn oeua uligbok rmtedesired the from blocks building molecular determine to chemistry reticular in used pathway General Chemistry: Reticular 2 2 B B N 3 4 5 TA(6)BDA (5)ETTA (4) (3) N H H N COF-66 N B(OH) B(OH) 2 2 HO HO OH OH H H HPE .GNRLBACKGROUND GENERAL 2. CHAPTER 2 2 N N Yaghi . [(ETTA)(BDA) NH NH 2 2 2 ] imine O O 6 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. aeo Dfaeok,ol igelyr r eind ec,dffrne a vnocrfrframeworks the for in occur However, even can topology. differences chosen to Hence, a due designed. fit design are topology to layers same monomers the single design featuring only to frameworks, tool 2D a of is case chemistry reticular conclusion, In fe eut nalyrdsrcuedet h strong the to due structure layered a in results often ehncladacietrlsaiiy[][1 1] samjrt fCFlnae n ooesfeature monomers and COF-linkages of majority both a with framework As the [13]. endow that [11] blocks [9] sp building stability aromatic architectural from and built mechanical commonly are COFs of Structures Topologies put interest 2D particular with discussed 2.3.1 be will and structures structures, COF 2D 3D layered and are 2D topology. five chapter, diamond which this the of In on reported nets. been 3D have are COFs for four topologies different nine date, To Structures COF 2.3 otpoietrpeettvsi O-hmsr.Hwvr w ieettpso eaoa Oscan COFs hexagonal of ( types staggered different a two either However, featuring obtained COF-chemistry. be in representatives prominent most eie qaesae rcrosalwtepeaaino q-tplg sur atc)CF.I this In COFs. to lattice) tuned (square be topology can sql- or available of readily preparation often the are allow which precursors used, Square-shaped be can desire. precursors aromatic simple cases, many 2 hbiiain atdge faoaiiyi anandtruhu aoiyo h rmwr,which framework, the of majority a throughout maintained is aromaticity of degree vast a -hybridization, • • • • • iue23sosrpre DCFtplge.Hxgnlsrcue hb oecm)aeaogthe among are honeycomb) (hcb= structures Hexagonal topologies. COF 2D reported shows 2.3 Figure c g q x kdg hxl sql kgm hcb lcrnmcocp SM,tasiso lcrnmcocp (TEM), microscopy electron transmission (SEM), microscopy electron tp5 hrceiaino h bandframeworks obtained the of Characterization 5: Step tp4 h O ssnhszdb tthn oehrtemlclrbidn lcstruhcovalent through blocks building molecular the together stitching by synthesized bonds is COF The 4: blocks. Step identified, building are poly-aromatic geometries large, determined previously to the leads to often correspond which that equivalents their Molecular and 3: geometry Step their number large extension, a of considered, was points exist. connectivity topologies of just if possible number because of crucial their is on information edges. This evaluated their angles. are at idealized up vertices them The breaking embedding 2: by symmetry Step vertices highest into the that, dissected on is Based topology chosen. the be to of has part topology framework target A 1: Step via ikgsdsusdi h etchapter. next the in discussed linkages iue2.3: Figure DCFTplge:Tems omn2 O topologies. COF 2D common most The Topologies: COF 2D e.g. e.g. tcigeffects. stacking O-)o nelpe ofrain( conformation eclipsed an or COF-1) π − π -interactions. via odrXrydffato PR) scanning (PXRD), diffraction X-ray powder HPE .GNRLBACKGROUND GENERAL 2. CHAPTER tcetera et [9]. e.g. O-)[0.In [10]. COF-5) 7 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. tblt n rsalnt a efudwe oprn ieetlnae Fg .)[8 [13]. chemical [18] between thermal 2.5) tradeoff stability, (Fig. a linkages general, chemical different In as comparing worse. when such or found better properties be the can specific outstanding for crystallinity the – linkage, and in affected stability the results be and can on time crystallinity Depending same and the stability at COFs. bonds reversible of of properties capability error-checking the in results Dfaeokadwsrpre by reported was and framework 3D n ftemi hrceitc fCF sta hyaelinked are they that is COFs of characteristics main the of One Linkages Dynamical 2.4 the channels from large with resulting structure hindrance only framework date, open steric To an The in [17]. [15]. results interpenetration reported. PMDA of with been tetraaminoadamantane degree has of the varying imidization PI-COF-4, higher by COF, the controlled 3D block, be building non-interpenetrating can the one interpenetration larger However, the – possible. blocks is building interpenetration nine-fold to up COFs, r eeal obtained generally are olwn schemes, following iue2.4: Figure 2.4. in shown as date. topology to diamond literature a use of featuring the majority products notably, the of in Most preparation resulted the synthesis. blocks facilitates COF building systems are linear 3D such which with in Using blocks, combination required building in date. precursors aromatic to units rigid polyhedral reported tetrahedral on been the of based have for generally few available is a COFs not only of 2D, usually synthesis than the topologies 3D before, more mentioned far As are there theoretically though Even Topologies 3D 2.3.2 precursors three [15]. featuring quaternary between synthesized angle, a and and and designed type trigonal were linkage [14]. COFs a of [10] multinary hexagonal, terms of framework a in set a – links, A same such used). the of are always formation molecules not the the where allow nets are angles, to (these bond perfectly nets both align requires transitive designing to it in have as lies Both demanding, challenge more The Yaghi length. even precursor. linker is trigonal as porphyrins a dual) well functionalized and (Kagomé as hexagonal of topology a preparation kdg- of the a preparation of requires the design often The and demanding phthalocyanines. more or is design precursor case, O-0,afaeokbsdo er(-mnpey)ehn n eehhlcadhd,wstefirst the was aldehyde, terephthalic and tetra(4-aminophenyl)methane on based framework a COF-300, ute xaddterneo osbe2 O oooisatrrprigtesnhssnon-edge synthesis the reporting after topologies COF 2D possible of range the expanded further A DCFTplge:Shmtcrpeetto of representation Schematic Topologies: COF 3D B) = igedaodui eland cell unit diamond single a via eesbeogncratos hsde o nyalwfrcvln od,btalso but bonds, covalent for allow only not does This reactions. organic reversible C B Uribe-Romo C) Dntokcmrsdo hs uligblocks. building these of comprised network 3D a tal. et A) igettaoa uligbokadisrpeetto nthe in representation its and block building tetragonal single a 1] u ote3 aueo hs imine-based these of nature 3D the to Due [16]. HPE .GNRLBACKGROUND GENERAL 2. CHAPTER via yai oaetbns(Cs,which (DCBs), bonds covalent dynamic 8 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. )[9 )[6 )[0 )[1 )[2 )[3 )[24] h) [23] g) [22] f) [21] e) [20] d) [16] c) [19] b) 2.5: Figure Linkage Type C B C O N C COF ikr:CFlnesadcaatrsis nomto nteesseswr eie rmtectdltrtr.a [10] a) literature. cited the from derived were systems these on Information characteristics. and COF-linkers Linkers: (23) (21) (19) (17) (16) (12) (14) (12) (11) (7) (8) (7) O O O O X CN CHO B B O OH OH OH OH H H H H 2 2 2 2 HO HO N N N N Boronate Ester Phenazine Boroxine Triazine Imide Imine C=C C-C O N B (24) (22) (20) (18) (15) (13) (10) O O (9) B O N N N B N O O N O N B HPE .GNRLBACKGROUND GENERAL 2. CHAPTER and physicalstability chemical stability:excellent thermal stability<450°C crystallinity: poor chemical stability:nonereported thermal stability<250°C crystallinity: notreported chemical stability:high thermal stability<400°C crystallinity: poor 1M NaOHandorganicsolvents chemical stability:1dayinwater,1NHCl, thermal stability850°C crystallinity: moderate systems, sensitivetobase chemical stability:betterthanboron-based thermal stability500-600°C crystallinity: good systems chemical stability:betterthanboron-based thermal stability<500°C crystallinity: good acid, base,atmosphericmoisture chemical stability:sensitivetowater,alcohols, thermal stability<500°C crystallinity: excellent acid, base,atmosphericmoisture chemical stability:sensitivetowater,alcohols, thermal stability<600°C crystallinity: excellent hrceitc References Characteristics b) d) g) h) e) a) c) f) 9 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. agn from ranging oadtoal nrdc yrx rusadhne nuehdoe odn Fg .)[27][28]. 2.6) (Fig. bonding hydrogen derivatives induce phloroglucin interactions. hence, using by and hydrogen-bonding achieved groups internal was hydroxy COFs of introduce imine-based introduction additionally of to the stability the to improve due to means stability COFs Another chemical imine improved show conventional COFs, imine-linked to of compared subclass a COFs, Hydrazone-linked blocks. building by iue2.6: Figure h otcmol sdCNlne ytm r mn-ae Os( COFs imine-based are systems linked C-N used commonly most The Linkages applications. C-N industrial for stability desired 2.4.2 the lack still COFs boron-based date, to [26]), length various sdsusdi h rvoscatr h rtgnrto fCF eebsdo ooi cdbuilding acid boronic on based were COFs of generation by first reported the were chapter, and previous blocks retaining the still in while discussed chosen, As be Linkages can B-O linkages possible of 2.4.1 array wide a 2.5, formation. bond Fig. the in in reversibility shown As linkages. eea rusatmtdt ov hspolmuigvrossrtge ( though, strategies Even various framework. using the problem of this deterioration the solve lead to can attempted alcohols groups even several and acids Furthermore, systems. odnainprnrto partner condensation hra n hmclstability chemical and thermal etr xeln eesblt n ro-hcigcpblt eutn nhg rsalnt swl shigh as well as crystallinity high in resulting (500-600 capability stability error-checking thermal and reversibility excellent feature Yaghi nti hpe,tems omnyue O-ikgswl edsusd ihseilfcso imide- on focus special with discussed, be will COF-linkages used commonly most the chapter, this In ytm ftesm yea hw n(i.26A r utemr tbedet eoeo tautomerism, keto-enol to due stable furthermore are A) 2.6 (Fig. in shown as type same the of Systems 1]adcwresadaebsdo nadmn odnaino mn n leyecontaining aldehyde and amine of condensation aldimine an on based are and coworkers and [10] mn Os ytei ceefrtepeaaino mn COFs. imine of preparation the for scheme Synthetic COFs: Imine i) B A efcnesdssesover systems self-condensed OHC HO (11) OH CHO 2)(12) (25) via iii) ◦ H-bonding. C OH CHO borosilicates CHO 2] nteohrhn,ti eesblt eut nrte moisture-sensitive rather in results reversibility this hand, other the On [25]. ) Yaghi (13) N H H 1] ae nbrncaisavreyo Oscudb synthesized be could COFs of variety a acids boronic on Based [10]. 2 2 N B) N ovninlimine-linkage. conventional (12) via odnaino ooi cd ihslnl.Teesystems These silanols. with acids boronic of condensation ii) ytm sn aehladohrdhdoyseisas species dihydroxy other and catechol using systems A) HPE .GNRLBACKGROUND GENERAL 2. CHAPTER O-bsdo hoolcndrvtv oimprove to derivative phloroglucin a on based COF- N H N e.g. HO O e.g. O-0) hc eedesigned were which COF-300), (26) (27) O OH NH N tautomerism enol keto- nrdcn ly hisof chains alkyl introducing O OH N H N 10 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. oa ufc Os ao atri h nouaiyo hs ytm stesrgl ooti highly obtain to [30]. struggle frameworks the crystalline is highly systems of formation these rearrangement, proper the of of for probability unpopularity the imperative reducing the is irreversible almost in which are factor bonds C-C major the as A systems crystalline COFs. surface as to Glaser n eiyeewt sqioiea ai aayta eprtrsbten200 between temperatures at catalyst basic a NMP The in as dianhydride) isoquinoline product. (pyromellitic with favored PMDA mesitylene and thermodynamically and tris(4-aminophenyl)amine the using being reported phthalimide were PI-COFs with first temperatures elevated at possible are nyafweape fCClne Oseit n oto hs ytm eeprepared were systems these of most and exist, COFs linked C-C of examples few a Only Linkages C-C proceeds it 2.4.4 possible, is correction error although that suggests, [17]. slower which slower inherently is systems, much PI-COFs imine crystalline reasonable comparable of for formation for allows the than synthesis that the suggest, in studies employed PXRD However, temperature high reversibility. the with combined solvents of combination ewe uttd fpsil pce sepce teeae eprtrsi h rsneo ae oee,teasneo water of absence the However, base. a of presence the in temperatures elevated phthalimide at of expected formation is the species possible favors of multitude a between iue2.7: Figure by introduced First system. imine-linked to COF next based are C-N (CTFs), bonding frameworks researched hydrogen triazine most through covalent the stability as maximizing COFs to hence, referred and often keto-form COFs, the Triazine-linked in [29]. locked be to system the allowing oaetceity oee,dpnigo h odtoso h omto,iiefraincnb carried be can formation imide [9]. formation, 2.7) the (Fig. of conditions dynamic conditions reversible in the under studied been on out not depending have However, bonds imide chemistry. chemistry, Schiff-base covalent reversible on based are imines Whereas Linkages Imide 2.4.3 850 eutdi atitrs nteesses nte mrigcaso - ae ytm r phenazine- are systems based C-N of class extended emerging on Another based are systems. that these COFs in linked interest vast in preparation resulted their of ease the and ssoni i.27 h ecino hhlcahdiewt rmr mn,avreyo intermediates of variety a amine, primary a with anhydride phthalic of reaction the 2.7, Fig. in shown As ◦ C [21]. ) 2]culn ntesraeo usrt eutn ntodmninlnnsrcue loreferred also nanostructures two-dimensional in resulting substrate a of surface the on coupling [24] md omto ahas ecino hhlcanhydride phthalic of Reaction Pathways: Formation Imide Phthalic anhydride hhlcai 2-Carbamoylbenzoicacid Phthalic acid T 2)(9 (30) (29) (28) (31) O O H O O (29) 2 OH OH O O vrohrproducts. other over via H R-NH R-NH H + 2 yltieiaincmie ihhg hra n hmclstability chemical and thermal high with combined cyclotrimerization O 2 R-NH 2 π ssesrsligi xrml hral tbesses(pto (up systems stable thermally extremely in resulting -systems 2 hhlmd Phthalamide Phthalimide H 2 O (32) O O O O N T OH NHR R (28) R-NH HPE .GNRLBACKGROUND GENERAL 2. CHAPTER ntepeec fa mn.Acmlxequilibrium complex A amine. an of presence the in R-NH 2 T 2 H 2 O Thomas n ookr 2] CTFs [22], coworkers and O O ◦ C NHR NHR ≤ T ≤ via 250 Ullmann ◦ C This . 11 or Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. Wasse ytei sitrsiga tcnb mlydframliue( multitude a for employed be can systems. it synthesized as conventionally than interesting area Interestingly, is surface significantly. synthesis BET time higher MW-assisted reaction significantly the a reduce showed to COFs allowing obtained way, the solvothermal a in COF-5 of preparation yia xeiet rmtcntie ( nitriles aromatic experiment, typical rai oyes(Os n Oscudb rprd[] oprdt ovteml oohra or multigram ionothermal a force. solvothermal, on driving to COFs main the produce Compared as to force alternative mechanical [8]. eco-friendly using prepared an by is scale be method could this COFs synthesis, by microwave-assisted and conventional pioneered less (POPs) though, the years of polymers recent one organic still In is COFs. scale, prepare industrial to an means on process traditional a although Mechanochemistry, Synthesis Mechanochemical 2.5.4 [11]. products purer in results generally and systems irwv-sitdsnhsso Oswsfis nrdcdi 09by 2009 in introduced first was COFs of synthesis Microwave-assisted Synthesis Microwave 2.5.3 [32]. oohra ytei a sdby used was synthesis Ionothermal Synthesis Ionothermal optimal solvent the of 2.5.2 find variety to wide needed a is Hence, experiments of reaction. part amount slow a significant a only a ensure as [31]. that solvents, COFs to system indicating the organic time employed, of any several be formation at with can the dissolved systems washing in is be role after shall precipitate crucial monomers crude obtained a the the are play of before Solvents COFs days extraction. designed soxhlet several The employing for often temperatures solution. elevated allowing the hence, at and from solvothermal kept vessel filtered the conventional is escape a system can’t water In The the released cycles, the linkages. freeze-pump-thaw reversibility. that several ensure of After to majority sealed system. are solvent the capillaries defined for employed a in suitability dispersed its are monomers to the due synthesis COFs of preparation the h at n uicto rcs iia oteoeepoe nslohra ytei.I eea,CTFs general, a In as synthesis. well solvothermal as out in solvent, washing employed one a after the obtained as to are acts similar CTFs chloride process prepared Crystalline zinc purification a reversible. the and be process, salts to this the cyclotrimerization In the time. enable to of catalyst periods extended for reacted and ovtemlsnhsswstefis ehditoue by introduced method first the was synthesis Solvothermal Synthesis Solvothermal 2.5.1 synthesis microwave-assisted following synthesis, The ionothermal discussed. synthesis. synthesis, are mechanochemical solvothermal COFs and of discussed: synthesis be the will towards methods techniques synthetic conventional Synthesis chapter, COF this In in Methods Synthetic 2.5 via oohra ytei hwpoe rsalnt than crystallinity poorer show synthesis ionothermal Thomas e.g. ,-iynbnee eedsovdi otnZnCl molten in dissolved were 1,4-dicyanobenzene) n ookr opeaetefis eotdCF 2] na In [22]. CTFs reported first the prepare to coworkers and Yaghi Banerjee HPE .GNRLBACKGROUND GENERAL 2. CHAPTER e.g. 1] n a ic enwdl sdfor used widely been since has and [10], mn rbrnt-se ae COFs based boronate-ester or imine Cooper n ookr,avreyo porous of variety a coworkers, and e.g. n ookr 3]frthe for [33] coworkers and ooie imine, boroxine, 2 t400 at etc )of .) 12 ◦ C Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. oeua egtiiecmonsi h 90.Ti rvdta trigfo nahdieadan and anhydride an 2003, in from Later, starting possible. that was conditions proved hydrothermal This under imide 1990s. an of the formation in the amine compounds imide weight molecular ihteecpino Os r omdb odnainratos(e i.2.9). Fig. (see reactions them, condensation of by most formed diverse, are quite are MOFs, materials of these ( exception though [34] the Even gemstones with [36]. synthetic (MOFs) of frameworks preparation metal-organic and the [35] including place take to reactions eslcle uolv.Ti uoeospesr lost oeit h yrtemlram niae by 2.8). indicated (Fig. realm, hydrothermal diagram the phase into the move in to area allows grey pressure the autogenous This autoclave. called vessel yrtemlsnhssof synthesis Hydrothermal t dpaini rai ytei a o ucsfluntil successful not materials, inorganic was of synthesis synthesis the organic for in used routinely adaptation been its has (HTS) synthesis hydrothermal though Polyimides Even of Synthesis Hydrothermal 2.6.1 2.9: Figure in dispersed (>100 are temperatures compounds elevated starting to tool the heated powerful experiment, is a typical mixture and a the formation In and mineral water materials. natural the crystalline by highly inspired obtaining technique for a is (HTS) synthesis Hydrothermal Synthesis Hydrothermal 2.6 iue2.8: Figure nteH eielqi n aeu hs oxs.Teecagseal uttd fchemical of multitude a enable changes These coexist. phase gaseous and liquid regime HT the In yrtemlSnhsso Zeolites: of Synthesis Hydrothermal hs iga fWtr h yrtemlrgm,starting regime, hydrothermal The Water: of Diagram Phase A HO 3)(4 (35) (34) (33) HO Si OH OH e.g. elt spsil oreyo iasaM Moura M. Hipassia of Courtesy - possible is L Zeolite -H 2 O HO HO Si OH O A) Si OH OH odnaino iii cdt iiii cdadfrhrcnesto osilica. to condensation further and acid disilicic to acid silicic of Condensation OH -n H > T 2 O Morton HPE .GNRLBACKGROUND GENERAL 2. CHAPTER 100 ◦ C SiO ne uoeospesr naclosed a in pressure autogenous under ) ◦ C 2 and B 3]rpre h ytei flow- of synthesis the reported [37] p t,i niae ytega area. gray the by indicated is atm, 1 > e.g. Zeolite L urzcytl) zeolites crystals), quartz Hodgkin [38] 13 B) Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. iue2.12: Figure 2.11: Figure 2.10: Figure introduced H hence and polyimides of preparation the for 2.10). HTS (Fig. use (HTP) successfully polymerization to hydrothermal able were coworkers and erae,wihrslsi esplrslet oreyo iimM Unterlass. M. Miriam of Courtesy solvent. polar less a in results which decreased, hsrne hsdciei h oi rdc 4]rslsi infiatylwrplrt fwtr–water 2.13). – water Fig. (see of increased polarity within is lower compounds change significantly organic significant a of show in solubility not results the does [42] hence, phase and product – gas ionic apolar the the more in of becomes decline constant This dielectric static range. the this time, same the At rsaln PPPI. crystalline ec,pesr sbitu ntesse safnto of function a as system the in up built is pressure Hence, ytei famliueo rai ml oeue ( molecules [40]. small frameworks organic even of multitude a of synthesis nuneo h iudpae oal,tecag ftedeeti osati h iudpaei fthe of is phase liquid ( the solvents in organic constant common of dielectric the range the to the phase of compared into gaseous the change diminishable moves the is and the it phase and as Notably, 2.13) gaseous importance, liquid phase. utmost the the Fig. on liquid Both effect in the the on shown significantly. however, influence (as drops conditions, HT significantly phase by aqueous increased influenced the is are of product [41] ionic constant the dielectric importantly, Most change. smnindbfr,hdohra ecin r are u sn ae at water using out carried are reactions hydrothermal before, mentioned Conditions As Hydrothermal under Water 2.6.2 obtained. sbnfiilfravreyo rai ecin Fg .2 nldn odnain,deprotections, which condensations, catalyst, including base and 2.12) acid (Fig. an reactions both organic as acts of [43]. conditions variety HT a under for water beneficial Hence, is time. same the at solution 2 N h hnei h oi rdc eut na nrae muto ohH both of amount increased an in results product ionic the in change The eetdvlpet ytegopof group the by developments Recent 3)(37) (36) NH yrtemlP Synthesis PI Hydrothermal eioeDe eioedeobtainable dye Perinone Dye: Perinone T ffc nPlrt:Shmtcrpeetto fwtra 300 at water of representation Schematic Polarity: on Effect - HTW 2 + HOOC HOOC COOH COOH H via 2 O h ooe atRue eea Isnhssemployed synthesis PI General Route: Salt Monomer the Unterlass H 3 N via N 3)(39) (38) O N yrtemlsnhssi Wpoeue i-adtas eioeare perinone trans- and Cis- procedure. MW a in synthesis hydrothermal monomer salt NH (41) hwdta T ol utemr euiie o the for utilized be furthermore could HTS that showed e.g. 3 HOOC OOC i.21) oyes[] yrdmtras[9 and [39] materials hybrid [7], polymers 2.11), Fig. T O N N ne hs odtos ait fproperties of variety a conditions, these Under . HPE .GNRLBACKGROUND GENERAL 2. CHAPTER COO COOH ◦ C yrgnbnsaeboe,itrcin are interactions broken, are bonds Hydrogen . H 16 bar e.g. T -4n H 2 O, 200°C 100 > 2 ctntie M rNMP). or DMF acetonitrile, O 3 O e.g. + ◦ C n OH and o h ytei fhighly of synthesis the for napesr vessel. pressure a in polyimide − N O O (40) osi the in ions tcetera et O O N 14 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. iimM Unterlass. M. Miriam 2.13: Figure ihTmeaueWtr eprtr eedneo ae rprisudrhdohra odtos oreyof Courtesy conditions. hydrothermal under properties water of dependence Temperature Water: High-Temperature HPE .GNRLBACKGROUND GENERAL 2. CHAPTER 15 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. T Motivation and Aims 3 Chapter n h vlaino hi sblt sCFpeusr.UigDTssol lo h obnto of combination of the properties gas-storage allow and should catalytic DATzs with Using PI-systems (DATzs) of precursors. diaminotriazines capabilities COF of high-performance triazines. synthesis as the the - usability with worlds their concerned two of was and networks evaluation project obtained this the the of of and part morphologies the second study The to Furthermore, measured frameworks. (TGA). was analysis (SEM) thermogravimetric microscopy and electron (PXRD) scanning diffraction X-ray powder (FTR-IR-ATR), mode eeplmrzdwt MA M n eltcai MlA,rsetvl.Teotie oosorganic precursors porous amine obtained The The respectively. achieved. (MellA), analyzed due be were acid planar frameworks should mellitic crystalline almost geometries and and is polymers PMA different TrisAPM PMDA, Hence, with whereas polymerized geometry, hindrance. were tetragonal steric a reduced features the TAPM to tris-(4-aminophenyl)methane cho- chosen. and were amine-precursors (TAPM) were different tetrakis-(4-aminophenyl)methane us- (TrisAPM) two by literature, Namely, techniques the harmful in investigation. environmental reported for PI-COFs and few toxic sen a otherwise only to are alternative there green As HTP. a ing find to was goal The tion. i rjc ie osnhsz h rtP-ae oaetogncframeworks organic covalent PI-based first the synthesize to aimed project his via 16 Fourier rnfr nrrdsetocp sn ATR- using spectroscopy infrared transform via yrtemlpolymeriza- hydrothermal Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. nNaNO on mentioned the to contrast stark elevated in at lies water polymerization only required Hydrothermal are requiring temperatures isoquinoline conditions, High frameworks. as such conventional such reversibility. catalysts the of as required in well synthesis the as lies NMP, ensure the or frameworks outstanding to for DMF PI-based as order their such of in solvents Especially, employed disadvantage high-boiling hence, be major and discussed. to The have were interest. that COFs of conditions PI-based harsh are of stability chemical properties and the thermal chapter, previous the In ih9%yedadaon 5 uiy(codn oGM) h eane a eatiue oresidual to attributed ( be procedures can reported remainder other obtained The to was compared GCMS). superior TPM to proved resulting (according furthermore moiety purity The approach This 95% chlorine around acid. intermediate. the and hypophosphinic substitute yield and to 90% conditions temperatures chloro- with cleaved acidic high from subsequently was under (TPM) at moiety isoamylnitrite tetraphenylmethane used amino The using of is intermediate. preparation aniline 4-(aminophenyl-trisphenylmethane the a step, in with first resulting starts a 4.1, In Fig. triphenylmethane. in shown synthesis, The TAPM of Preparation 4.1.1 . 2 Chap. in discussed was obtained are conditions hydrothermal how h eie product. desired the 4.1: Figure Frameworks PI-based MellA as well 4.1 of as synthesis PMDA the PMA, in using precursors out amine carried as were TrisAPM polymerizations and TAPM The into respectively. study out. a carried thesis, was the PI-COFs of part this Within Discussion and Results 4 Chapter 4)(43) (42) Cl 2 rprto fTP:Tefis tpsostefraino P olwdb irto n usqetrdcintowards reduction subsequent and nitration by followed TPM of formation the shows step first The TAPM: of Preparation ,a hs hwdlwrcneso,a ela oetm-osmn workup. time-consuming more a as well as conversion, lower showed these as ), DMF 2) H H isoamylnitrite 2M HCl/MeOH 1) aniline 3 PO 2 SO 2 4 TPM 90% HNO AcOH via 3, Ac 2 O, yrtemlPolymerization Hydrothermal 17 O 2 N T TNPM saslet h ocp fHS t s,and use, its HTS, of concept The solvent. a as (44) NO NO 2 2 60% NO 2 Pd/C, MeOH,H 2 H 2 N TAPM (45) NH NH e.g. 2 2 95% based NH 2 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ftemtaecro n ec t erhda tutr.TiAMwscoe sana oprsna it as comparison neat a as 4.2). chosen (Fig. was TAPM TrisAPM to structure. compared tetrahedral flexibility its more hence features and carbon methane the of rcro ihnafwhours. few a within precursor sdsusdpeiul,TP sahgl tbepeusrfauigasp a featuring precursor stable highly a is TAPM previously, TAPM:PMDA discussed of As Characterization and worst Polymerization the in and 4.1.4 time-consuming be oxidation. to of proved degree treatment minor the a in after resulted TAPM case drying However, product. purer AMi ihysal rai oeueadddntso n erdto pnsbetn tt prolonged to it subjecting upon 250 degradation any to show up not of did and conditions molecule hydrothermal organic stable highly a is Conditions TAPM HT under TAPM 4.1.3 expected. be can structures APCRBP10. network (CCDC-identifier: anions chlorate with species carbocationic a as found be only could TrisAPM CCDC. on found as 4.2: Figure AMwscoe sapeusrdet h osblt ogt3 ewrsa euto h sp the of result a as networks 3D get to possibility the to due precursor a as Precursors chosen was as TAPM TrisAPM and TAPM 4.1.2 in filtration resulted required solvent the as from MeOH resulting losses with tin(II)chloride- only autoclave the hydrogen with Celite. with a GCMS) over reduction using NMR, (reaction loading, However, yields Screened Pd/C HCl. quantitative products. almost and different of iron tetra-(4-nitrophenyl)methane mixture and using a of hydrazine and to reduction hydrate led with approaches The reduction conventional as included method. challenging Hence, conditions quite this product. be using solemn to the avoided proved as (TNPM) be obtained was could species purification nitro desired tedious the conditions, suboptimal indicate might hw iteflxblt.T ute eueteflxblt n ooti ii n tbentokPD was PMDA network stable and rigid a obtain to and flexibility the reduce further To flexibility. little shows oee,a a eepce rmtesrcueo h rcros atydffrn rdc emtisand geometries product different vastly precursors, the of structure the from expected be can as However, nascesv tp P a irtduigfmn HNO fuming using nitrated was TPM step, successive a In tutr fTiAMadTP:Cytlsrcuedt rmTiAM[5 n AM[4 CD-dnie:RARRAE) (CCDC-identifier: [44] TAPM and [45] TrisAPM from data structure Crystal TAPM: and TrisAPM of Structure B A T fu o250 to up of ◦ C oee,eprmnsa 300 at experiments However, . ◦ C ol eue orcytlietepeusrt bana obtain to precursor the recrystallize to used be could HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER 3 n Ac and 2 ◦ /cH.Atog il f60% of yield a Although . O/AcOH C 3 eutdi abnzto fthe of carbonization in resulted yrdzdcro etethat centre carbon hybridized 3 hybridization 18 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. oyeiain(HP a rvosydsrbdby described previously was (sHTP) polymerization rH odtosaeue.Nntees td noterato ierqie o ulP omto was formation PI full for required time long 200 reaction As that conventional the formation. surprising whether into PI regardeless not study of ease – a is the Nonetheless, systems evaluate it to PI this, used. conducted crystalline are to highly conditions Due in generate HT byproducts to or discussed. possible required were of are frameworks variety times and the reaction and PI-networks reversibility of of synthesis importance the the Previously, temperature. reaction AMadPD r ihysal rcros oee,udrH odtos h rcrosaeexposed are precursors the conditions, HT high under only However, not precursors. stable to highly are PMDA and TemperatureTAPM and Time Reaction of Evaluation 4.1.5 amorphous. entirely are diffractograms products reactor, PXRD reaction MW comparing MW the when the as seen of products, be nature autoclave easily the stirred can with the This products reversibility, microwave to networks. hindered the speed regular Due of reaction of increased formation hours. this that the 24 found to we of Yet, crucial maximum faster. complete a to to able were limited reactions were reactions MW the polymerization. 4.3: Figure H 180 between conducted usually was HTP precursor. initial an as chosen rasirdM eco t230 at reactor MW stirred a or ne mes tes hscudesl eosre,we oigto moving when observed, be easily could This stress. immense under upeslto eutdi lc rcptt.I eeldta h rcptt orsoddt mixture a to The corresponded further. precipitate modes. investigate the ammonium to that by collected indicated revealed were powders. salt IR they brown monomer as observed, precipitate. and obtained be black imide be could of a to phase in products liquid the resulted the and solution of yellow purple color to in change change to solution a the As of color the in resulted Hence, speed. reaction the determine to used also 200 were to conditions heated these were synthesis, precursors PI the for conditions .) ait fitrsigpeoeacudb bevd isl,fl ovrina observed as conversion full Firstly, observed. be could phenomena interesting of variety A B.3). n oe t250 at more) and hs nig r utemr neetn si ae rud2husfrteatcaet ec h desired the reach lower chapter. to following at autoclave in the the begins for obtained in already hours were discussed polymerization 2 precipitate further around that is and takes indicating, that it solution as reaction purple temperature, interesting side deep furthermore a a are Yet of findings occurrence These hours. the 4 indicating only process after the achieved be already can abnzto curdwti nhu frahn ecintemperature reaction reaching of hour an within occurred carbonization 2 N oyeiaini h uolvswr are u vrpoogdproso ieo pt as whereas days, 9 to up of time of periods prolonged over out carried were autoclaves the in Polymerization TAPM (45) NH NH oyeiaino AMwt MA T fTP ihPD.Atcae n Wratr eeue o the for used were MW-reactors and Autoclaves PMDA. with TAPM of HTP PMDA: with TAPM of Polymerization 2 2 T NH ◦ u lot neteeybscadaii niomn.Hne h rcrosare precursors the Hence, environment. acidic and basic extremely an to also but , C 2 lorsle nprilcroiain hrfr,200 Therefore, carbonization. partial in resulted also + O O O PMDA (46) ◦ ◦ C C . O O o -4hus(eetdsetacnb on nteapni . and B.2 appendix the in found be can spectra (selected hours 2-24 for O H 180 -250°C 2 O, Baumgartner ◦ C na uolv a hsna h eea reaction general the as chosen was autoclave an in HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER N tal. et N N T T hss-aldsub-hydrothermal so-called This . ≤ T ≤ 250 > T R 4] oigto Moving [46]. ogtm xoue( days (5 exposure Long-time . ◦ N O O C 250 TAPM-PI ◦ a hsna general a as chosen was C (47) seily t300 at Especially, . ◦ C O O sn nautoclave an using N t R 0hours 10 > via N N ATR-IR 19 ◦ N C Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. aminophenyl)methane. 4.4: Figure to according cation TrisAPM work, C). a this and be to to B Under found 4.4 advance observed. were (Fig. In was which analysis obtained phenomenon XRD has. be same they single-crystal TAPM could the A) – crystals TrisAPM and that 4.4, green to attempted four conditions, related was the (Fig. certain TAPM closely of dyes of more polymerization general compared methanarylamine hydrothermal in moieties of the are 4-aminophenyl reminiscent dyes three is violet have crystal itself However, only color violet. The crystal as by-product. such or intermediate an of T Synthesis HT from TrisAPM-Carbocation 4.1.6 erpae.Hdohra oyeiain ntesm aho speiul eotdwr odce at conducted were reported to previously had 200 as experiments and fashion the 190 same conditions, 180, the certain 170, in under 160, polymerizations intermediate this Hydrothermal of repeated. formation be the of hypothesis our prove nyapial o ierplmr.Hwvr siae o ewr oyescnb made. be can polymers network for estimates However, polymers. linear for applicable only h T oad I saplcnesto,acag nsocimtyrsligfo h laaeo an of cleavage the Since from discussed. resulting stoichiometry be tem- in to lower change have impact at a TAPM reaction greatly polycondensation, on the would a based during moiety is formed frameworks aniline PIs be of towards can synthesis HTS intermediate the the carbocationic on a implications that the proven peratures be Synthesis could Framework on it Species As TrisAPM-Cation the of Implications 4.1.7 on implications severe has HTP for used conditions reaction Assuming frameworks. the NMR. 2N TAPM-based to under of according of form which obtained HTS to be in the able could conducted species is cationic were carbocation desired experiments the The present, that reaction. cleavage reagent the the to a As added without aniline. was of conditions HCl elimination HT catalyzed acid under the possible enable to was Pt and HCl utilizes procedure Gomberg’s eie rsasaan oee,tecytl eeol banda ypouti o ils(1 %). (<10 by yields 1898 low in in reported by-product been has a TAPM as from obtained moiety only aniline were an crystals of cleavage the Catalytic However, again. crystals desired A N eprl oo fbt h ouina ela h rcptt tlwrato ie niae h formation the indicates times reaction low at precipitate the as well as solution the both of color purple he oee,tecniin ftefraino adcytl eentaporaeydcmne.Hne to Hence, documented. appropriately not were crystals said of formation the of conditions the However, (48) N rsa iltDe n h TrisAPM-carbocation: the and Dyes Violet Crystal Cl N C) hw h rsP-abcto sotie rmhdohra ytei sgencrystals. green as synthesis hydrothermal from obtained as TrisAPM-carbocation the shows N rsa iltTrisAPM crystal violet ◦ C (48) o ecintmsrnigfo o2 or.I a osbet banthe obtain to possible was It hours. 24 to 2 from ranging times reaction for N Cl Carothers N X n B H p = 2 N = qain(q .) eeal paig h qainis equation the speaking, Generally 4.1). (Eq. equation + 1 N + 1 0 q N (49) − NH 0 A) − N q 2 2 hw omrilcytlvoe dyes. violet crystal commercial shows qp HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER NH 2 C Gomberg 4] However, [47]. B) hw tris(4- shows (4.1) (4.2) 20 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. iue4.5: Figure qain X equation. ftecroainsest edpnigo lwn onteiiilrato pe ylwrn the lowering by speed reaction initial the down formation slowing the on amorphous As depending only be phenomenon. cases to this most through seems in explained carbocation precursors be the can these of obtained, using were while networks that crystalline fact partially the or would Hence, TrisAPM:PMDA as stoichiometry. impact 2:3 great a a has require TAPM:TrisAPM-cation:PMDA of stoichiometry mixed a to (1:2) ec euigtehaigrt,i em esbet r oices h nta ecinsed Performing speed. reaction initial the increase to 80 try at to flask stirred feasible a seems in it reaction the rate, heating the reducing hence nta fPD oehneterato pe.H xeiet ntesm aho sfrTAPM:PMDA used for was as fashion PMA same formation the its in experiments minimize HT to speed. least reaction conducted. at the were or enhance TrisAPM-carbocation to PMDA the of of instead formation the avoid To TAPM:PMA of Characterization and Polymerization 4.1.8 the in precursor hydrolyzed partially opened a be having to of have risk not does the dianhydride reduces the PMA place. as using first speed Furthermore, reaction process. the the increases in PMDA of instead PMA using Fg .)rvae,ta rsaln oyeswr obtained. were polymers crystalline that revealed, 4.6) (Fig. bantecroaincseisbtaan nyamxueo h Iwt h abctoi pce ol be could species carbocationic the to with conducted PI were the of ( experiments mixture conditions further a certain Hence, only at again, obtained altogether. but species avoided carbocationic be the not obtain could but reduced significantly okn tFg . n a aiyse htmvn rma pia tihoer o TAPM:PMDA for stoichiometry optimal an from moving that see, easily can one C 4.5 Fig. at Looking safis eut h omto faprl ouinadplmra o ecintimes reaction low at polymer and solution purple a of formation the result, first a As oeetne ecin eutdi rw oyes swstecs o AMPD.Hwvr PXRD However, TAPM:PMDA. for case the was as polymers, brown in resulted reactions extended More n T . ereo oyeiain ..etn frato.q. oa ai ftemonomers. the of ratio molar q... reaction. of extent p... polymerization. of degree ... iAMcto n t mlctos cee of Schemes Implications: its and risAPM-cation T 160 = ◦ C nteohrhn,dentla otedsrdpoutete.However, either. product desired the to lead doesn’t hand, other the on ◦ C , t R or and hours 2 = A AMand TAPM B HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER TrisAPM-carbocation. T 170 = ◦ C , t R hours). 2 = C) iga eie rmCarothers from derived Diagram t R or was hours 2 = T and 21 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ∼ iue4.6: Figure . Å). 4.1 = iha mrhu akrud niaigta h ees ecinmgtb oefvrda certain a at being favored reflection lowest more the be with reflections might same reaction the show reverse general, in the diffractograms, that the Furthermore, indicating point. background, amorphous an with rsalnt eae oeicnitnl.Ti a paeta at as apparent was This inconsistently. more behaves crystallinity 4.4 rsalnt ftesse em oices with increase to seems system the of Crystallinity ° (2 # Cu-K , AMPAXD PXRD XRD: TAPM:PMA α d ,

hkl Intensity [a.u.] 99Å,ga eeto at reflection gray Å), 19.9 = NSTR, NSTR, NSTR, NSTR, NSTR, NSTR, NSTR, NSTR, NSTR, 01 02 30 25 20 15 10 5 01 02 30 25 20 15 10 5 t t t t t t t t t R R R R R R R R R = 48h,200°C = 72h,200°C = 96h,200°C = 24h,200°C = 120h,200°C = 144h,200°C = 168h,200°C = 192h,200°C = 216h,200°C fTP:M oyeiainpout eoddatr19dy.Lws eeto oag)at (orange) reflection Lowest days. 1-9 after recorded products polymerization TAPM:PMA of ∼ 19.3 2 ° θ (2 Cu-K C # Cu-K , t α R d , swsepce.Hwvr after However, expected. was as , α hkl HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER [°] . )adbakreflection black and Å) 4.6 = t R 10hmn ape eeobtained were samples many h >120 ∼ 21.6 ° (2 # t Cu-K , R 2 h 120 = α d , 22 hkl Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. h yohss htap-ffc sehnigterato pe nteerypaeo h polymerization the of phase early the allows in This speed crystallization. polymerization. reaction faster 1:2 the to the enhancing leads of is then signals pH-effect and the a to that compared hypothesis, pronounced the more are general in reflections 4.1. es oee,uo vlaigPR hne ntedffatga eeimdaeyvsbe(i.4.8). (Fig. visible immediately were diffractogram 4.5 the pow- around in brownish reflection changes in lowest TrisAPM:PMA. resulting PXRD the TAPM:PMA of evaluating Again, of polymerization upon polymerization the However, 1:2 for aniline the needed the ders. to as stoichiometry similar well 2:3 as proceeded moiety remaining polymerization TrisAPM a the The ac- of in carbocation into resulting the take both hence theory, stabilize in moiety, to should, needed stoichiometry moiety This PMA the conducted. count were stoichiometry 2:5 a with polymerizations iue4.7: Figure 4.4 around utemr oprdt oe opud Fg .)otie fe T fTP ihptai anhydride phthalic with TAPM were of spectra HTS The after 4.7). obtained 4.7) (Fig. 200 modes (Fig. (autoclave, compound, C-N model the a and to imide-carbonyl compared the furthermore importantly most present, being modes al 4.1: Table spectrum. the in and molecule the in highlighted are modes imide Characteristic TAPM. with anhydride 74cm 1714 ndaieo r niaieo imides. of indicative are of inidcative ofrhrivsiaewehrtefraino h abcto ol etknit con,TAPM:PMA account, into taken be could carbocation the of formation the whether investigate further To T-Rsetao h rdcssoe itet onn ieec ewe n nte ihalexpected all with another one between difference none no to little showed products the of spectra ATR-IR − A 1

Rmds hrceitciieI oe ssoni i.4.7 Fig. in shown as modes imide-IR Characteristic modes: IR Transmission [%] epcieyaepeetwt oohrmd niaigby-products. indicating mode other no with present are respectively AMPAIR: TAPM:PMA NSTR NSTR apeC=Omd [cm mode O = C Sample ° 003500 4000 (2 NSTR, Modelcompound,NSTR, # Cu-K , ◦ C t t R R , t t 4h17 n 7116 1285 1366 1721 and 1774 h 24 = 2 74ad12 361278 1366 1720 and 1774 h 120 = R R = 72h,200°C 2hu ecin.Acmaio ewe Iplmr tdifferent at PI-polymers between comparison A reaction). hour 72 = α ,wl ihnteramo Dcvln rai frameworks. organic covalent 3D of realm the within well ), A) T-Rsetu fTP:M oyeiain h niaieiiecroy oe t18 and 1780 at modes imide-carbonyl indicative The polymerization. TAPM:PMA of spectrum ATR-IR 0020 0010 1000 1500 2000 2500 3000 Wavenumber [cm t R = 72h,200°C ° (2 # Cu-K , − 1 mode N - C ] α swl ihnteramo DCFssesadthe and systems COF 3D of realm the within well is ) -1 ] B HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER seilyteC=Oa 70ad11 cm 1714 and 1780 at O = C the Especially . 1 B) [cm oe opudobtained compound Model − 1 mode N - C ] 500 B Model compound O O N 2 [cm O O via t − R N N T fphthalic of HTS 1 ] ssonin shown is − O O 1 oe are modes N O O 23 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. iue4.8: Figure reflection (2 hw nFg . eetossa h aewt h oetrflcinsilbigaon 4.38 around being still reflection lowest the with same the stay reflections 4.9 Fig. in shown eecridotwt 0m fsleti natcae nysalaonso rdc eeotie.To obtained. were product of amounts small only experiments a autoclave, conventional concentrations, different an As at mmol/L. in samples 50 solvent the to of of 10 mL homogeneity between 10 ensure - with concentrations out low carried in were out carried usually is Yield HTP Reaction of Evaluation diffractograms. polymerization 1:2 4.1.9 the in found ones the with align perfectly reflections the Interestingly, rm1 o3 mlL natcaeat autoclave An mmol/L. 30 to 10 from Cu-K # Cu-K , α d , hkl ∼ α d , AMPA25XD PXRD XRD: 2:5 TAPM:PMA . Å). 3.2 = 19.4

hkl Intensity [a.u.] ° 96Å,rdreflection red Å), 19.6 = (2 NSTR, NSTR, NSTR, NSTR, # Cu-K , 01 02 30 25 20 15 10 5 01 02 3 25 20 15 10 5 α d , t t t t R R R R hkl = 96h,200°C = 24h,200°C = 48h,200°C = 72h,200°C . ) lc reflection black Å), 9.5 = ∼ ircormo AMPAatrHPfor HTP after TAPM:PMA of diffractogram 5.5 ° T (2 R 200 = # Cu-K , 2 α ◦ θ C d , Cu-K C ∼ hkl and 21.8 58Å,bu reflection blue Å), 15.8 = t ° R (2 2 eecoe srato aaees As parameters. reaction as chosen were h 120 = # HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER Cu-K , α [°] c α cenn a odce with conducted was screening d , t hkl R - as oetrflcin(orange) reflection Lowest days. 1-4 = . )adgenreflection green and Å) 4.1 = ∼ 10.0 ° (2 # Cu-K , α d , ° hkl (2 . ) gray Å), 8.8 = # ∼ 0 c Cu-K , 27.5 ranging ∼ ° (2 4.5 24 α # ). ° , Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. iue4.9: Figure ) lc reflection black Å), tihoer t200 at stoichiometry ∼ 2 n h ieetcnetain niaig httecnetainlmthsntbe ece yet. from concentrations reached the been increasing not after has significantly limit increased concentration reactions the the that of yield indicating, overall concentrations the different However, the and h 120 5.7 oprn h ircorm,teei omjrdffrnebtenete ogtm ecin fu to up of reactions long-time either between difference major no is there diffractograms, the Comparing ° (2 # Cu-K , AMPAXD-C - XRD TAPM:PMA α d , ∼ Intensity [a.u.] ◦ hkl 21.7 C and 55Å,bu reflection blue Å), 15.5 = NSTR, NSTR, NSTR, NSTR, NSTR, ° (2 t R # Cu-K , 2 na uolv.Lws eeto (orange) reflection Lowest autoclave. an in h 120 = 01 02 30 25 20 15 10 5 01 02 30 25 20 15 10 5 t t t t t n.Sre:PX ftecnetainsreigTP:M bandatrHPwt 1:2 with HTP after obtained TAPM:PMA screening concentration the of PRXD onc.-Screen: R R R R R α = 120h,200°C, = 120h,200°C, = 120h,200°C, = 120h,200°C, = 120h,200°C, d , hkl . )adgenreflection green and Å) 4.1 = ∼ 10.1 ° 2 (2 θ # Cu-K C Cu-K , c c c c c = 25mmol/L = 15mmol/L = 20mmol/L = 30mmol/L = 10mmol/L α d , hkl α HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER ∼ . ) ryreflection gray Å), 8.7 = [°] 27.4 ° (2 ∼ # 4.4 Cu-K , ° (2 # α Cu-K , d , hkl . Å). 3.2 = ∼ α d , 19.0 hkl ° 06Å,rdreflection red Å), 20.6 = (2 # Cu-K , α d , hkl 4.6 = 25 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. noprtsTiAM(rne nteui el eutn nsm ereo iodrwiertiigoealdaodi structure. diamondoid overall retaining while disorder of degree some in resulting cell, unit the in (orange) TrisAPM incorporates 4.10: Figure incorporating still while retained be could structure diamond the idealized of be an most could expected, TrisAPM-carbocation 4.10 4.10, than the species. in Fig. how TrisAPM cell shown In shows the unit As that angles. smaller model shown. higher a a is to and in incorporated reflection model lowest resulting TAPM:PMA species the theoretical fashion TrisAPM a of postulate semi-regular formed structure, shift to the a the impossible that, in explain almost is would system is hypothesis Moreover,which it current the our hence, products. in However, and crystalline incorporated formed the correctly. are TrisAPM in system of the resulted amount of that the structure syntheses which the quantify the tested, to conditions in any impossible case under the is the formed between be it also pristine can be was the species should TrisAPM-cation this of size the that reflections that cell suggests, found, unit lowest not was the do the It that simulations between them. indicating the of lies system 4.11 two reflection interpenetrated Fig. lowest two-fold in the The shown and were as data. framework systems However, experimental interpenetrated cell. the three unit with and diamond system align expected diamond Iqbal the pristine Mohamed on A Musthafa based by systems. simulated group optimal our according of in product PXRDs conducted same generate were the to yield simulations to Theoretical seem measurements. polymerizations TAPM:PMA PXRD all to chapters previous the COFs in shown TAPM:PMA As Simulated with the Comparison of pH the material, reaction. 4.1.10 starting better of overall amount an increased in the resulted to and due altered that was made, solution be initial can assumption the case, this 44% bu) n rgnlbidn lc ( block building trigonal a and (blue)) t1 mlLt 1 t3 mlL nrae ilswieu-cln aebe bevdbfr.In before. observed been have up-scaling while yields Increased mmol/L. 30 at 81% to mmol/L 10 at yohtclCFIcroaigteTrisAPM-carbocation: the Incorporating COF Hypothetical A = = e.g. rsP-at(rne)i h olwn schemes. following the in (orange)) TrisAPM-salt B A) HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER ersnaino ergnlbidn lc ( block building tetragonal a of Representation B) hw yohtclmdlthat model hypothetical a shows e.g. TAPM 26 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. imn-iesrcueadtie rpeadqarpeitreertdsrcue.SmltduigMtrasSui 2017. Studio Materials using Simulated structures. interpenetrated quadruple and triple twice, and structure diamond-like iue4.11: Figure AMPAXRD TAPM:PMA Intensity [a.u.] Experimental, 01 02 30 25 20 15 10 5 iuain xeietlPR pcrmo AMPAcmae otertclmdl fapristine a of models theoretical to compared TAPM:PMA of spectrum PXRD Experimental Simulation: 01 02 30 25 20 15 10 5 t R = 120h 2 θ Cu-K C α HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER [°] 4-fold interpenetrated 2-fold interpenetrated 3-fold interpenetrated non-interpenetrated 27 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. a sd h ecinpoeddi h aefsin ootmz h S eprtr,TAanalysis TGA temperature, SSP the optimize To fashion. same the in proceeded reaction the used, was via iue4.12: Figure as required system TAPM:PMA the the in for monomers case PIs desired the linear was the this of combining Indeed, polymerization as overnight. simple and and them as well stirring synthesis is, and the flask salt a in monomer in a group stoichiometry generating our theory, within In used [7]. previously were salts Monomer Salt Monomer TAPM:PMA 4.1.11 t pe naywy omte hte ihvcu (10 high-vacuum whether matter No way. any in speed its eu.AShekfls a hre ihtemnmrslsadhae otmeaue ewe 0and 80 between temperatures to heated and salts monomer the SSP simple with a charged using was off, 200 was flask stoichiometry Schlenk the A although performed, Salt setup. was Monomer salts TAPM:PMA monomer the the of of Polymerization Characterization and Polymerization 4.1.12 purple. to precipitate the olwdb hnetwrsga-s fe eea or,dpnigon depending purple hours, to several off-white from after changed gray-ish initially towards Color change observed. a be by could followed color in transition same the temperature, mn oe r nieyasn Ap.B6.I aycss h rprto fmnmrslscnbe can salts monomer of – 40 preparation between the temperatures to cases, heating many when However, In stirring. while 80 B.6). suspension the (Appx. heating by absent accelerated entirely vacuum high are or oven modes an amine in dried be not can salt monomer the that fact the to polymerization. accounted in be result can would peak this as water broad The stoichiometry. atra higher at faster ◦ T-Ro h ooe at hw h xetdamnu oe n abnlmds Furthermore, modes. carbonyl and modes ammonium expected the shows salts monomer the of ATR-IR 1 C ◦ -M Fg .2,PR Fg .3 n G Ap.B4adAp.B.5). Appx. and B.4 (Appx. TGA and 4.13) (Fig. PXRD 4.12), (Fig. H-NMR C ata oyeiainocre ihnhus niae yacag nclro ohteslto and solution the both of color in change a by indicated hours, within occurred polymerization partial .078 8.00 7.84 4.00 o 4o 2husudrrdcdpesr.Uo etn h ooe needn fteused the of independent monomer the heating Upon pressure. reduced under hours 72 or 24 for ...... 2.0 2.4 2.8 3.2 3.6 4.0 4.4 4.8 5.2 5.6 6.0 6.4 6.8 7.2 7.6 8.0 1 -M fteotie at ofimdte12socimty h ooe atwscharacterized was salt monomer The stoichiometry. 1:2 the confirmed salts obtained the of H-NMR AMPAMnmrSl NMR: Salt Monomer TAPM:PMA T rsoe tlower at slower or HOOC OOC T ult ftevcu sdi h ecinddntaetteSPor SSP the affect not did reaction the in used vacuum the of Quality . 1 -M fteTP:M ooe at h inl nert oad 1:2 a towards integrate signals The salt. monomer TAPM:PMA the of H-NMR COO COOH chemical shift[ppm] H 3 N NH NH − 3 3 3 HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER br rcnetoa ebaepm vacuum pump membrane conventional or mbar) NH 3 HOOC OOC H 2 O T h hnei oo occurred color in change The . COO COOH DMSO 0 28 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. eutn oyeiae,sldsaeplmrztsadahdohra oyeiain ascomparison. polymerizations hydrothermal a and polymerizates solid-state polymerizates, resulting 4.2: Table 4.2. Table in compiled are measurements TGA ◦ oyeiainhssatd televated At started. has polymerization rdcsobtained products a odce,wihrvae htSPocr taon 170 around at occurs SSP that revealed which conducted, was eutn nfl ovrinwti 0huswt ofrhrcagst h oye vni etfratotal a for kept if even polymer the at to SSP changes above, further mentioned no As with hours. hours 65 20 of within conversion full in resulting rmo-ht oprl a eosre.Cytliiyo h ooe ati o eanddrn h SSP. the during retained not 11.4 is at salt reflections monomer change small the color with of a background Crystallinity bath, amorphous oil observed. mostly the be in A can flask purple Schlenk to the submerging off-white after from Immediately polymer. desired the towards ulplmrzto sntpsil steoptimal the as possible not is polymerization full (2 C # h mrhu akrudi lgtyicesdcmae otepitn ooe atidctn that indicating salt monomer pristine the to compared increased slightly is background amorphous the XDo h oyeiae a esrdadrvae hta low at that revealed and measured was polymerizates the of PXRD Cu-K , AMPAMnmrSl G:Plmrzto eprtr ftemnmrslsaddgaaintmeaueo the of temperature degradation and salts monomer the of temperature Polymerization TGA: Salt Monomer TAPM:PMA α sotie fe S Fg 4.13). (Fig. SSP after obtained is ) via T n S hwdtesm hra tblt at stability thermal same the showed SSP and HTP apetype Sample S,150 SSP, ooe at3 o/ 7 527 531 172 172 200 NSTR, mol/L 30 salt Monomer mol/L 10 salt Monomer S,200 SSP, ◦ ◦ T C C ◦ , , C T f10-200 - 170 of t t , R R t eodthe beyond R 2h-526 - h 72 = 8h-532 - h 48 = 8h-535 - h 48 = T SSP ◦ sntytrahd oee,at However, reached. yet not is C T T oyeiainpoed atadquantitatively and fast proceeds polymerization , SSP SSP HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER ° eut nafs n uniaieconversion quantitative and fast a in results [ ◦ (2 C ◦ ] # C Cu-K , Ap.B4adAp .) ohthe Both B.5). App. and B.4 (Appx. T D T [ R ◦ C α ,17.1 ), and ] T D t ≈ R ° ( 530 (2 t R # 0h, 20 = Cu-K , t ◦ R C 0h, 20 = eut fthe of Results . α T n 22.4 and ) 100 = T 100 = ◦ 29 C ° ) Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. iue4.13: Figure Cu-K h optimal the α d , hkl T . )adbu reflection blue and Å) 5.2 = SSP XRD n S t200 at SSP a and fteMnatadisSP:PR esrmn ftepeusrTP,tepitn ooe at S below SSP a salt, monomer pristine the TAPM, precursor the of measurement PXRD SSPs: its and MonSalt the of Intensity [a.u.] Monomer salt SSP, SSP, TAPM 01 02 30 25 20 15 10 5 01 02 30 25 20 15 10 5 t t R R = 20h,100°C = 65h,200°C ◦ C oetrflcin(orange) reflection Lowest . ∼ 22.7 ° (2 # Cu-K , 2 α θ d , Cu-K C hkl . Å). 3.9 = ∼ 10.6 α HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER ° [°] (2 # Cu-K , α d , hkl . ) e reflection red Å), 8.3 = ∼ 17.1 ° (2 30 # , Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. h apesosbt rsaln at rgntn rmteTiAMsl n mrhu pee rmtepolymerization. the from spheres amorphous and TrisAPM-salt the from originating parts crystalline both shows sample The ooe atcnit ftn,agoeae particles. agglomerated tiny, of consists salt monomer a eosre ihu sn irsoedet h ieo h rsasfre n hi pia properties. optical their and TrisAPM-salt formed the crystals as the expected, of size be the the could to hence what due microscope with polymerization, a align the using perfectly without to observed findings accounted be initial can be These can PI. which the visible, of TrisAPM- are formation the spheres from originating amorphous particles Secondly, rhombohedral rod-like, cation. large of consisting phase crystalline a Firstly, iue4.14: Figure and formed be can stoichiometry, wrong polymerization. the the of with stages although later salt, the monomer given in which a if polymerized species, at that TrisAPM-carbocation frameworks is polymerizes a crystalline shown, and of process to was formation heating transform it the initial to Thirdly, to the able leads during reaction are formed formed is side which PI is a desired networks, the Secondly, amorphous Firstly, time. form products. several sufficient to of formation able the is to leads and TAPM:PMA of HTP stands, it Micrographs As SEM of Evaluation 4.1.13 infiatfaue.Hwvr h rdc fe t200 at h 2 after product the However, features. significant [46]. all obtained morphology soluble on at not SSP dissolved are and be polymers polymerization and to hydrothermal by oligomers polymerization, monomers reported when sub-hydrothermal the been polymerization of for previously the effects has high of effect stages too This later is occur anymore. concentration also the can where SSP samples, time. for occur can SSP h obnto fteetrepeoealast neetn nig ihrsett h morphology the to respect with findings interesting to leads phenomena three these of combination The B A via E fteMnatadSotPolymerizations: Short and MonSalt the of SEM E.Temnmrsl Fg .4AadB ossso iyagoeae atce ihu any without particles agglomerated tiny of consists B) and A 4.14 (Fig. salt monomer The SEM. T ≈ 170 ◦ C elblworHPtmeaue oee,as However, temperature. HTP our below well , 10 μm 30 μm C) and D) E irgaho h AMPAplmrzto t200 at polymerization TAPM:PMA h 2 the of micrograph SEM : A) Baumgartner and D C ◦ B) C E irgaho h AMPAmnmrsl.The salt. monomer TAPM:PMA the of micrograph SEM : HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER SRrato hw w ao morphologies. major two shows reaction NSTR tal. et uigasuyfcsigo the on focussing study a during T above T SSP 30 μm r employed, are 10 μm 31 ◦ C . Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. iue4.15: Figure esebigteshrsfudi h irgah ftesotrato ieeprmn.A higher At experiment. spheres time amorphous reaction with short co-exist the phases of major micrographs these the of random in a Both Secondly, found found. spheres particles. angular be the intergrown can reassembling large sheets of consisting thin-walled C) of and network (A phase bulky a Firstly, (A-D). bandb using by obtained ieetplmrh ftesm oye eeotie.A ait fdffrn hnmn cu during occur phenomena surprising. different not of is variety morphologies a of sample that As hypothesis variety single the obtained. the a for TAPM:PMA were in allows of polymer This found HTP same be diffractogram. the PXRD only same of not the polymorphs could to different morphologies amount they different samples, though, between Even also but issue. an been have might eogt h 2 ,200 h, 120 the to belong irgah hnesgicnl.Aan ewr-iemrhlg a efud oee,cmae to compared however, found, be can morphology network-like a lower Again, the significantly. change micrographs atce a efud h atrmgthv omddet S sahigher a as SSP to due formed have might latter The found. be can particles B A E irgah ftepout bandatrHPaedpce nFg .5 irgah (A-D) Micrographs 4.15. Fig. in depicted are HTP after obtained products the of micrographs SEM c SEM apetentoki oecnesd utemr,asmlrblymrhlg fcondensed of morphology bulky similar a Furthermore, condensed. more is network the sample f10hu oyeiae:SMmcorp fTP:M at TAPM:PMA of micrograph SEM Polymerizates: hour 120 of c 0mo/ ttesm odtos w ao hsscnb on ntemicrographs the in found be can phases major Two conditions. same the at mmol/L 30 = 30 μm ◦ C 10 μm SRrato with reaction NSTR D C c 0mo/,wees( n )acutt h sample the to account F) and (E whereas mmol/L, 10 = 100 μm HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER 30 μm c 0mo/ ( mmol/L 10 = F E A-D c and ) a sdadsolubility and used was c 0mo/ ( mmol/L 30 = 30 μm 50 μm n F and E c the , 32 ). Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. hc lgswt h hra eopsto eprtr fteTP:M ytm T system. TAPM:PMA the of temperature decomposition thermal the with aligns which ihrrato ieo ihtecnetainue ntereaction. the in used concentration the with or time reaction either iue4.16: Figure should B). PMDA 4.16, as such (Fig. co-monomer cell stiff unit very a hexagonal with a TrisAPM combination in possible. in result polymerizate which TrisAPM-cation structure possible planar a almost of an structure features the into assumptions for allow might TrisAPM:PMDA of T Characterization and Polymerization 4.1.14 B7 r eyicnitn.A oecnetain,terflcina . (2 results 8.9 the at However, reflection obtained. the be concentrations, could some – At angle, yields better inconsistent. in and very whether organic crystallinity high evaluate are covalent higher to (B.7) too conducted – a TAPM was way in screening for concentration is as result A effects didn’t reflection similar polymer. solid, lowest linear a crystalline the pronounced. in a presumably formed, more yielding and framework be although slightly polymerization, should become the cell angles that unit higher indicating hexagonal at a reflections that the Considering and increases background amorphous oei sntpeet nteohrhn,alsmlsbsdstelws ocnrto ( concentration lowest the besides samples all hand, other the On present. not is it some aecniin NSTR, – conditions same polymerization. TrisAPM:PMDA after eeto sitrsig h atta tocr sa mrhu ao swl sta ti tl o ihfor high too still framework. is crystalline it a that obtain as to well needed as are halo, improvements amorphous further an that as indicates cell occurs unit it hexagonal that a fact the interesting, is reflection nadtoa oe nl eeto t6.7 at reflection angle lower additional an .7sostePR fteTiAMPD oyeiae tdffrn ecintms l diffractograms All times. 8.9 reaction at different at reflection polymerizates same TrisAPM:PMDA the the show of PXRD the shows 4.17 i(-mnpey)ehn TiAM a hsna h eodaiebsdpeusro neet sit as interest, of precursor based amine second the as chosen was (TrisAPM) ris(4-aminophenyl)methane G esrmns(. n .)sosatemldcmoiintmeaueo rudT around of temperature decomposition thermal a shows B.9) and (B.8 measurements TGA rsP,atog etrn oeflxblt,i uta tbeudrH odtosa AM ec,the Hence, TAPM. as conditions HT under stable as just is flexibility, more featuring although TrisAPM, rsP n hoeia rmwr Structure: Framework Theoretical and TrisAPM A H 2 N T R 200 = TrisAPM (49) ° NH (2 ◦ 2 C # , Cu-K , t R NH - as–wr sdi h oyeiaino AMPD.Fig. TAPM:PMDA. of polymerization the in used were – days 1-9 = ° 2 (2 α # n 20.5 and ) Cu-K , A) α tutr fTrisAPM. of structure sa mrhu ao vntog hsadditional this though Even halo. amorphous an as ) B ° (2 HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER # Cu-K , α .Hwvr ihincreasing with However, ). B) # hoeia eaoa ntcl obtained cell unit hexagonal theoretical Cu-K , = PMDA = TrisAPM α srtie,weesat whereas retained, is ) D c intcag with change didn’t mlL show mmol/L) 1 = D 530 = t R the , ◦ 33 C , Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. oee h mrhu aoa ihrage nrae swell. as increases angles higher at halo amorphous the however iue4.17: Figure PRXD

fteTiAM MAsse tdffrn ecintms rsalnt em oices ihrato time, reaction with increase to seems Crystallinity times. reaction different at system PMDA TrisAPM: the of Intensity [a.u.] NSTR, NSTR, NSTR, 01 02 30 25 20 15 10 5 01 02 30 25 20 15 10 5 t t t R R R = 24h,200°C = 48h,200°C = 72h,200°C 2 θ Cu-K C α HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER [°] 34 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. htteotmlrato odtoswr o e Ap.B1) G aasosarte o decomposition low rather a shows data TGA B.10). (Appx. T met of not temperature were conditions reaction optimal the that cdat sacr ytmisl hc hudi hoyyedavr ml ntcl.PR ftesystem the of PXRD cell. unit small mellitic very the a system yield TrisAPM:MellA theory the in in should 20 whereas, around which halo cell amorphous itself unit an system only larger shows core a a in as resulting acts linker acid a as acts PMDA polymerization. nter euti itr fiieadaielnae uigtepolymerization. the could during which linkages autoclave, amide the and in imide of started of stabilty already mixture have polymerization thermal a could The the in decarbonylation that result decarbonylation. and theory indicate of low in could degree quite unknown be PXRD to an the seems in of MellA resulting nature successful amorphous completely the not with was together loss mass static iue4.18: Figure PMDA opened of already stability features thermal also the than and lower PMDA is to if acid compared carbonization mellitic (MellA) in molecule of acid resulting planar stability mellitic thermal more paper, However, On and moieties. sturdier precursor. anhydride stable a highly is a 4.18) is TrisAPM chapter, (Fig. previous the in TrisAPM:MellA mentioned of As Characterization and Polymerization 4.1.15 rsP:el hudas euti eaoa ntcl.Hwvr nteTiAMPD system TrisAPM:PMDA the in However, cell. unit hexagonal a in result also should TrisAPM:MellA rsP:el hoeia Structure: Theoretical TrisAPM:MellA A H 2 N D 480 = TrisAPM (49) NH ◦ C 2 T swl sasai asls ewe 0 n 400 and 200 between loss mass static a as well as , 220 > NH 2 ◦ C sue rif or used is ° (2 A HOOC HOOC tutr fTiAMadmlii acid. mellitic and TrisAPM of structure ) # Cu-K , MellA (51) COOH COOH α t niaigta eesblt ftesse stolwor low too is system the of reversibility that indicating ) R COOH COOH asa 200 at days 3 > HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER B ◦ C . B) hoeia eaoa ntcl after cell unit hexagonal theoretical ◦ C = MellA = TrisAPM Ap.B1) This B.11). (Appx. 35 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. h rsa tutr ftemnmrsl n r faopost eicytlientr.Teporducts The obtained ones nature. the semi-crystalline as to stability amorphous thermal of same are the and showed reproduce salt to SSP not monomer after over found the TAPM:PMA were obtained of products of suspension polymerization structure the a found and stirring crystal performed was by the was obtained it SSP be Furthermore, could temperature. room stoichiometry measured. the at 1:2 night as be a impossible with can’t seems salt reaction hypothesis monomer the in the this a in As proving that during incorporated However, formed was found. cell. TrisAPM-carbocation it be unit that of altered could made amount an fit be in can no resulted assumption hence that the and revealed system formed, systems was TrisAPM-carbocation X-ray expected interpenetrated the the the of cases to obtained, variety all diffractograms was a obtained system the and crystalline Comparing a systems As systems. the diamond-like However, simulated the avoided. to concentration. be of highest compared not yield the were overall could for diffractograms 80% the species to carbocation on lowest the effect the of positive for 40% formation a conditions. from has increased reaction reaction be same could the the which up-scaling reaction, at that obtain see systems to revealed to concentration possible also three even lower obvious was investigation of to it immediately The factor and compared a was case, crystallinity the by system higher was upscaled this with open was Indeed, systems the reaction obtained. The to be PXRD. could changing results the homogeneous of in whether found impact were The reflections crystalline investigations. when further in used was ihams h aetemlsaiiya AMPA oee,telws eeto t8,9 at reflection lowest the However, polymers TAPM:PMA. semi-crystalline as in stability resulted thermal PMDA same with the TrisAPM investigated almost of was Polymerization TrisAPM with these conditions precursor. of certain amine origin under TriAPM-carbocation, another the obtained the as as was of TrisAPM-carbocation seen formation a be the can As of SSP morphologies. combination and A polymerization hydrothermal polymerization. polymerization, the sub-hydrothermal of result a as morphologies AMPAsse,a tsostems rmsn rlmnr eut nrgrst crystallinity. to regards the in on than results focused preliminary stability be promising thermal should most lower investigation the shows Future shows TrisAPM:MellA MellA it conditions. framework. as as reaction proper system, nature a TAPM:PMA under amorphous it decarbonylate be purely consider would could of to halo and the high be PMDA if too to even be found Nonetheless, revealed, still were halo. furthermore would amorphous polymerizates screening it an concentration reflection as A proper obtained a be cell. can considered unit reflection hexagonal angle a lower a feature that should that framework a for carbocation The of species. instead carbocation PMDA the using of formation and the temperatures produced favor reaction be to lower reaction furthermore seem to initial can PMA the due species on reactions dependent anhydride is Slower open not species an the were carbocationic reaction. of product the the solemn cleavage of the formation of through as the speed obtained, species formed that this be seems obtain seemingly it to could that However, conditions crystals optimal species found. green date, TrisAPM-carbocationic To TAPM. of a from amount moiety be aniline a to small found conditions were certain which under that revealed investigation E irgah ftemnmrsl,a ela oyesa different at polymers as well as salt, monomer the of micrographs SEM rdc prrsnln) etrn hoiecutro,cudb confirmed be could counterion, chlorine a featuring (pararosaniline), product hwdol ata on rsalnt.Uo netgtn ecinseda neetn hnmnnwas phenomenon interesting an ( speed times PXRD reaction reaction However, investigating low formed. Upon very was For polymers. crystallinity. network PI found. no polyimide based a to TAPM:PMA indeed partial synthesize that only to indicate project showed ATR-IR able the as were of well We as part TAPM. stability, first of Thermal The polymerization synthesized TGA. the were PMDA, and on polymers PXRD with focussed organic ATR-IR, systems was porous using of based characterized variety aminophenylmethane and A different polymerization investigated. four hydrothermal were project co-monomer as the MellA of or part PMA this within summary, In Outlook and Conclusion 4.1.16 via cdctlzdeiiaino nln ne yrtemlcniin.The conditions. hydrothermal under aniline of elimination catalyzed acid t R 0hus upeslto n rcptt a band Further obtained. was precipitate and solution purple a hours) 10 < HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER t R and via via c hwavreyo different of variety a show M.A eut PMA result, a As NMR. T with HTP T ° D stohigh too is ≈ 530 via ◦ 36 C . Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. r14dcaoezn)aecmie ihdcadaieudrbsccniin oyedtedsrddi- desired the yield to conditions basic under dicyandiamide with combined are 1,4-dicyanobenzene) or Fg .0A.Tesnhsso Az olw h aebscpicpe rmtcntie ( nitriles Aromatic principle. basic same product the triazine follows desired DATzs the of yield nitrile synthesis to The The nitriles precursors. A). other as 4.20 two nature, with (Fig. aromatic reaction trimerization of a usually undergoes cyanides, functionality with synthesized are CTFs Synthesis Conventionally, Organic in Force Driving Strong a - Trimerization that linkers further. imide even incorporating performance while chemical associated and cases thermal use the potential improve the the would with and precursor COFs retained based triazine is triazine aromatic tunability Namely, Secondly, fully given. and feature is stable they polyimines highly or as via PIs a PI-Tz-COFs towards Firstly, polymerization of for interest. synthesis functionality of required the blocks for building investigation key for two chosen were (DATzs) Precursors Diaminotriazines COF as 2,4-Diamino-1,3,5-triazines 4.2.2 content. heteroatom high their 4.19: Figure storage energy gases, of storage and separation including applications of ( range wide a for attractive are Art CTFs the of State 2). high allow (Chapter 4.2.1 their which COFs to known of due are synthesis be 2) the interest (Chapter in will patricular imperative syntheses of precursors is of are which array COF and reversibility, wide as COFs decent a for Furthermore, 2,5-diamino-1,3,5-triazines well-known rather stability. of of chemical use and family thermal the a are especially CTFs and discussed. CTFs Science chapter, Materials this and In COFs in Triazines 4.2 aayi 5](e i.41) fseilitrs stehg irgncneto Ts hc soften is which or CTFs, system of the content of wettability nitrogen distribution the electron high the changes the affect which example, is for material, can, interest carbon N-doping special (HAE). a effect Of inside atom hetero strong 4.19). a with associated Fig. (see [51] catalysis r yteie ietyfo ynd rcrosadol e o-ietmtost noprt triazines incorporate to design. methods they precursor CTFs non-direct as special Usually, few material require scaled-up. only fascinating they industrially and as a be precursors known are can are cyanide CTFs that from properties, syntheses directly these their synthesized to while ability Due are stability the and [52][53]. enhance porosity [48] can high gases content feature store heteroatom to high material that a indicators of are there Furthermore, material. electrode e.g. h aapsto ftebneemit.Hne hsapoc ol lo h obnto ftoworlds. two of combination the allow would approach this Hence, moiety. benzene the of position para the o yrgnsoae[8 ra lcrd aeil 4],pooaayi 5]adee heterogeneous even and [50] photocatalysis [49]), materials electrode as or [48] storage hydrogen for plctosfrCF:Bt aayi n yrgnsoaeaeuo h otrsace s-ae o Tsdeto due CTFs for use-cases researched most the upon are storage hydrogen and catalysis Both CTFs: for Applications HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER e.g. h lcratv ufc of surface electroactive the e.g. benzonitrile 37 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. agraon fslet(.xcmae otecnetoa prah steratrhdt efildup filled be to had reactor required the after and as 85% slower approach) and is conventional 78 system the between MW minimum. to larger yield absolute compared the overall an (1.5x of an to solvent heating in Four of of the resulted procedure. amount case as 30-minute all larger the a increased, and a in in was product parallel microwave, of time in g a Reaction run 8.9 using yield were purification. to synthesis scale 10, the of that factor of of a limits by reactions up the scaled tesing was synthesis further the To BATB, DATz. the towards reacted methods. ieetceia edr hc a l edt h orsodn diaminotriazines. available corresponding readily the furthermore are to can tetracyanobenzenes lead which functionality even all or core, of may tri- degree triazine which di-, The the vendors Mono-, chemical to B.12). precursors. different corresponding specific changed (Appx. benzene using be medicine by the easily in tuned of can be application tuned position precursors for be para the can interesting DATzs the of be Hence, properties in could 4.21). UV/VIS residuals (Fig. example, different products For using possible of by cases. range use wide desired a their in results towards which used be can that rcdr.Snhsso l tutrsbsdstetri-DATz the besides structures all of Synthesis procedure. iue4.21: Figure 4.20: Figure microwave straightforward and quick a using out carried was from trimerization (adapted the procedure case, this In aminotriazine. oee,teei iiaini h aeo eti rh iyn-ytm,a nyoecaiemoiety cyanide one only as dicyano-systems, ortho certain of case the in limitation a is there However, h neetn ataottesnhsssoni i.42 isi h ierneo osbesubstrates possible of range wide the in lies B 4.20 Fig. in shown synthesis the about part interesting The B) B A H R= COOH,NO ytei fdaioraie sn yndsaddcadaiei Wprocedure. MW a in dicyandiamide and cyanides using diaminotriazines of Synthesis ytei fTizns ytei ceefrtesnhsso triazines. of synthesis the for scheme Synthetic Triazines: of Synthesis 2 imntizns ceeo ait fdffrn Az ayo hc r obtainable are which of many DATzs different of variety a of Scheme Diaminotriazines: N N N DATz (52) (19) (53) R =CN,NO R CN CN N R R NH 2 2 , NH various methods Methoxyethanol Dicyandiamide, KOH MW, 190°C 2, Ruiz-Osés COOH 2 , CHO H H 2 2 N N N N N BATB 5)(5 (56) (55) (54) N N N 5],t nuehg ilsadsotrato ie Fg .0B). 4.20 (Fig. times reaction short and yields high ensure to [54]), NH NH 2 2 R H 2 N H (55) OH N 2 N H N NH N pce eecnutda ato hsthesis. this of part as conducted were species 2 (20) N N N NH R 2 N H N N CN N N R N HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER N NH N NH 2 R N 2 NH A) 2 rmrzto fntie possible nitriles of Trimerization O O NH NH H via 2 N 2 2 N CN N N 0mnt microwave 10-minute a DATz (53) N NH R N N 2 NH NH 2 2 via various via 38 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. aiiyta h mn moieties. amine the than basicity Wva a hre ihtepeusr nsocimti mut.Wtrwsaddadtesystem the and added was or Water autoclave an amounts. Either stoichiometric systems. in based 180 precursors TAPM the to for case with heated the charged was was was as vial fashion MW same a the in attempted was HTP BATB of Polymerization Hydrothermal conventional of synthesis the on focusing focusses majority polymers. the that organic with other available available porous the literature is or on of publications 2,4,6-triamino-1,3,5-triazine, polymers amount of melamine, in For number limited large use a systems. a to similar only precursors hand or precursors is these DATzs based There of stability DATz polymerization thermal precursors. of the and on ideal variety chemical be a high should generate the they Considering to offer, was COFs. project of this synthesis of hydrothermal the aim the above, Derivatives mentioned and As BATB of Polymerization Attempted core. benzene 4.2.4 the from seen as axis the across tilt little only shows BATB that bevd utemr,n ecincudb bevduo digete xesPD u o1 q)or eq.) 10 be to could reaction. (up progress the PMDA reaction to when excess no However, system either eq.) the 7 adding to [56]. to upon AcOH reaction (up observed N anhydride the be 6 salt- phthalic to or could a excess HCl AcOH) reaction generating or conc. no This by or Furthermore, (HCl averted N react. acids be 2 observed. certain can cases excess either some adding moieties add in by the amine to could precursor than attempting the and basic the before melamine more of protonated with are species These working be core like when triazine will acetone. issue the nitrogens and of common could ring nitrogens a water derivatives the ring is with its the Hence, washing and that after BATB fact moieties. product the fact, amine to solemn In attributed the be obtained. as could was circumstances setbacks polymer all no under chosen, retained were be conditions which or used iue4.22: Figure Precursor – DATz BATB Versatile A - BATB 4.2.3 ovninlpolymerization. conventional to up stable thermally solvent. is a that as powder 2-methoxyethanol also dry crystalline It using white easily reaction can a deficient. BATB MW as electron 5-minute PIs. obtained of very a synthesis was by general the BATB conditions in enable should basic is that under and triazine, prepared each system be on push-pull two moieties, a amine features four system features the Hence, spacer. rsa -a ircin(CXD fBT rsasgrown crystals BATB of (SC-XRD) diffraction X-ray crystal i-24daio135tizn)bnee–faue w raiecrsconnected cores triazine two features – Bis-(2,4-diamino-1,3,5-triazine)-benzene AzadTertclPolymer: Theoretical and DATz ◦ C B A ≤ T B) R H hoeia AzPD oye ytm hc ol o eobtained be not could which system, polymer DATz:PMDA Theoretical ≤ 2 N 230 N N DATz (53) N R A) ◦ C eea Azsrcue lehglgt hw h igntoesta etr higher feature that nitrogens ring the shows highlights Blue structure. DATz General NH o pt as oee,n atrwihDT rcro was precursor DATz which matter no However, days. 3 to up for 2 O N O via HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER O yrtemlrcytliain[5 revealed [55] recrystallization hydrothermal DATz -Imide N O N (57) N R N O N O O N O T D via ≈ ihrhdohra or hydrothermal either 360 via ◦ benzene a C Single . 39 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. bevdadtepeusr eercvrdatrworkup. after recovered were precursors the and observed sdfrteatmtdplmrzto fBATB:PMDA. of polymerization attempted the for used 4.3: Table as result same the all different in However, six retained place. was of point. BATB taking total boiling Namely, reaction varied any and obtained. A was without were stability time polymerization cases solvent progress. hydrothermal Reaction on the reaction for depending procedures. described hinder hours literature previously severly 96 using and can screened 24 were water between 4.3) of traces (Tab. systems as solvent/catalyst use before dried were u intrsl ntefraino niiebsdCF h xeietwsas tepe ne HT unter attempted tested also were was systems experiment solvent The conventional COF. Five imine-based an hours. at of 72 autoclave added, an formation or were using the 48 solvents conditions for in the reflux result flask, species. to a didn’t are DATz in heated but bonds of combined was of polymerization were reaction acids. amount terephthalaldehyde the the carboxylic small and facilitate and than BATB a could reactive experiment, only species more typical hence, generally anhydride a and are of In Aldehydes solution instead in reversible. aldehydes that be is using to ensure, precursor Hence, reaction to of the sophisticated amount allow highly small to are a broken synthesis only times imine-COF all solvothermal at in systems Solvent synthesis. oto hs ytee eecnutduigBT steDT ytm oee,ohrDT systems DATz other However, system. DATz the as BATB using NO conducted as were such syntheses these of Most as well as NMP, or attempted. DMF, was as polymerization such Zn(OAc) conventional solvents LiBr, systems, boiling as DATz high such screened toxic, reagent the on a of relies any synthesis for polyimide work Conventional not did HTP As Derivatives its and BATB of Polymerization Conventional ieaueo Os ievreyo ytmdpnigsletmxue aebe eeoe htallow that developed as well been as have process, solvothermal mixtures a solvent through depending imine-COFs published of system all amounts of of small majority variety of vast preparation wide the the to A amount and COFs. systems on researched most literature the amongst are COFs based Imine BATB-COFs Imine-based of Synthesis Conventional 4.2.5 different. vastly is molecule the of environment chemical the though odtosUe nteCnetoa oyeiaino AztwrsIie:Cnetoa ovn n aaytsystems catalyst and solvent Conventional Imides: towards DATz of Polymerization Conventional the in Used Conditions 2 hzwr losree ne eti odtosbtdd’ hwayrato rgeseven progress reaction any show didn’t but conditions certain under screened also were PhTz ovn ytmraetrato ie[h] time reaction reagent system Solvent mdzl 72 24 24 24/48/72/96 24 - LiBr isoquinoline - - imidazole toluene DMSO/ NMP NMP Zn(OAc) NMP imidazole DMSO/ 2 T riounln.T nueotmlcniin,alslet n catalysts and solvents all conditions, optimal ensure To isoquinoline. or R 200 = ◦ C and t R 8o 2h oee,n ecinpors ol be could progress reaction no However, h. 72 or 48 = 2 HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER 24 via MW-assisted 40 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. oh ierplmr swl sntokssescnb yteie.Hwvr steeplmr could polymers these as However, conducted. were synthesized. investigations be further no can tunability. conditions systems conventional of network under degree as obtained high well only a as for polymers allows linear which Both, aldehydes), multifunctional or mono-aldehydes functionalized leye( aldehyde o 2hus ucinlzto spsil hog ohteDT ( DMSO DATz in the reflux both to through heated subsequently possible was is was flask and Functionalization a precursor this, procedure, hours. aldehyde standard to 72 and a Due DATz for In approach desired DATzs. goal. This the on the acetone. based with was in polymers charged system solubility functionalized the of imine-linked explains preparation an which the of obtained, facilitates requires formation were only polymers the weight systems as low-molecular these used, only Comparable Preparing were 4.23. equivalents reported. Fig. 2 in been however, occurred. shown have as aldehyde BATB of system the even equivalent aminal-linked with quite and an 1 reaction is melamine of some finding formation on that the This based be indicating systems to dissolved. acetone, Nonetheless, found in precipitate was observed. soluble the reaction was not The acetone, morphology is with in BATB change precipitate as a the interesting polymerization, washing the and in filtration DMSO upon pure using of case the ihtedsrdDT n leyepeusradwssbeunl etdt eu nDS o 2hours. ( charged 72 for DATz was DMSO the flask in reflux both a to procedure, through heated low- subsequently standard possible only was a is and this, In Functionalization precursor to aldehyde DATzs. and Due DATz facilitates on desired approach goal. based the This with the polymers acetone. functionalized was in of system solubility the preparation imine-linked explains the an requires which of obtained, only were formation systems polymers the weight these molecular Comparable as Preparing used, 4.23. were reported. Fig. equivalents in been occurred. 2 shown have aldehyde as BATB the of system even with equivalent aminal-linked and an reaction 1 melamine of some formation on that the based indicating be quite systems DMSO, to is Nonetheless, finding found in This was soluble observed. reaction dissolved. the be not was The could in precipitate is morphology the BATB However, acetone, in as with change species. interesting precipitate a the polymer polymerization washing any the and in filtration in upon DMSO result pure didn’t using imine-COFs of towards case BATB of Systems Aminal-linked polymerization towards The Derivatives and BATB of Polymerization 4.2.6 synthesized. be can systems network as well aaytssesue o h tepe oyeiaino BATB:terephthalaldehyde. of polymerization attempted the for used systems catalyst al 4.4: Table h oyeiaino ABtwrsiieCF intrsl nayplmrseis oee,in However, species. polymer any in result didn’t imine-COFs towards BATB of polymerization The C niin sdi h ovninlPlmrzto fDT oad mns ovninladhdohra ovn and solvent hydrothermal and Conventional Imines: towards DATz of Polymerization Conventional the in Used onditions e.g. =CO NO CHO, R= e.g. e.g. eehhlleyewe oyeie oehrwt AB noriiilexperiments initial our In BATB. with together polymerized when terephthalaldehyde eehhldhd hnplmrzdtgte ihBT.I u nta experiments initial our In BATB. with together polymerized when terephthaladehyde MO-72 72 72 48/ 72 48/ - - - AcOH 6N 72 48/ hydrothermal water- hydrothermal water- AcOH toluene 6N DMSO/ DMSO o o mesitylene dioxane/ ovn ytmraetrato ie[h] time reaction reagent system Solvent dclrbnee -rpnl-72 72 48/ - AcOH n-propanol 6N -dichlorobenzene/ n-propanol -dichlorobenzene/ 2 , etc. ,wihalw o ihdge ftnblt.Bt,lna oyesas polymers linear Both, tunability. of degree high a for allows which ), e.g. =NH R= HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER 2 NO , e.g. 2 =NH R= OH n h leye( aldehyde the and COOH) , 2 NO , 2 OH n the and COOH) , e.g. 41 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. partner. 4.23: Figure mnllne oyes ceai ytei fa mnllne oye ytmuigDTswt leye sreaction as aldehydes with DATzs using system polymer aminal-linked an of synthesis Schematic Polymers: Aminal-linked H 2 N N N DATz (53) R N NH 2 72 h DMSO, 180°C R-CHO N H N N N R N H R N H HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER Aminal DATz-Polymer N N N R N H (58) R N H N N N R N H R N H N N N R N H 42 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. tutr fBATB. of structure pedx(px ) CXDo ABrvae hti rsalzsa yrt n tlzn t hydrogen 4-NO its molecule. utilizing the and across hydrate a the tilt in as minimal and crystallizes shows 4.24 it also Fig. that BATB in revealed compiled capabilities. BATB are of bonding results SC-XRD the C). and (Appx. measured appendix was SC-XRD DMF. in recrystallization after iue4.24: Figure in recrystallization after (4- solid 4,4’-(6-(4-nitrophenyl)-1,3,5-triazin-2,4-diyl)-dimorpholine crystalline of case white the a In as NO obtained conditions. HT be under could water BATB previously Derivatives its mentioned and As BATB of Crystallography 4.2.7 eigbn oi n raue ihcytldniyo .82g/cm 1.4842 of density crystal high a freatures and motif hering-bond 2 hT)-apeusrseiclysnhszdfracoeainprnr-oag rsaswr obtained were crystals orange - partner cooperation a for synthesized specifically precursor a - PhMTz) rsa tutrsadMcorpso ABad4-NO and BATB of Micrographs and Structures Crystal C) irgah fBT crystals. BATB of Micrographs 2 PhMTz: HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER A) rsa tutr f4-NO of structure Crystal 3 . 2 hT rsalzsi an in crystallizes PhMTz 2 MPhTz. B) Crystal 43 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ytei a eneautd h Az wt h xeto fR OH eesynthesized polymer were in COOH) precursors R= of as exception usability the their (with DATzs and The synthesized evaluated. been been has has diaminotriazines synthesis of variety a summary, In Outlook and Conclusion 4.2.8 oyesa ela ewr oyescudb bandfauigahg ereo uaiiya ohthe both as use-cases. tunability desired of their degree towards high tuned a be featuring can obtained precursors linear be aldehyde stoichiometry the could adjusting and polymers Upon originated amine network precipitate oligomer. as this weight well that low-molecular found as aminal-linked was be polymers an It could of precursors acetone. using the formation with of than the washing case morphology from a the different filtration In of upon precipitate polymers. dissolved researched a desired that of most none the observed, formation However, of the the formation reported. catalyst amongst the are a in without systems furthermore resulted DMSO solvent/catalyst are systems of solvent/catalyst variety Imines tested wide the a synthesis. of hence, and their chemistry in COF reactivity in higher used feature linkers conventional are of which of preparation aldehydes, acids, the as case carboxylic As considered, the were reagents. than in polyimines the and possible, alongside not tested used polymerization was were were PIs conventional systems additives DATz-based to as solvent nor different different COFs, conditions HT of cases Neither variety triazine-imide similar both a successful. under of In polymerization not HTP HTS products. was However, the desired PIs initial the in of The species. yielded preparation precursors two the product. DATz for desired the synthesized used the of the previously in the properties use result (refluxing high-performance to didn’t approach the reaction conventional was combine MW the project COOH, the this R= as of of used, quenching case goal be after the to obtained In had were overnight) filtration. products precursors subsequent Pure and solvent. water hot as in 2-methoxyethanol using procedure MW scalable HPE .RSLSADDISCUSSION AND RESULTS 4. CHAPTER via uc and quick a 44 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. Polythiophenes atII Part 45 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. oynlnsrqiet eoiie obcm conductive. become to oxidized be to require polyanilines 5.1: Figure as such polymers sp traditional these a In of in conductivity structure. bound The molecular are their electrons solutions. at valence as looking the them to by polyethylenes, process compared explained advantage, to be biggest possibility can Their the polymers is semimetals. systems, or metallic metals to conventional, comparable conductivity feature materials C Polymers Conductive 5.1 Background General 5 Chapter odciiy ncnutv oyeso h te ad h oye akoefaue otnossp continuous a features backbone polymer the hand, other the on polymers conductive In conductivity. hi eue omi ools.Amjrgi nitrs a oee aattl 97 when 1977, till vacant however was interest in gain major A colorless. is on form depending reduced without groups their or several with systems into aromatic split on Letheby be based are which can polymers in ( polymers conductive band of heteroatoms conductive majority electronic general, The one-dimensional build-up. In a chemical form their [57]. p-orbitals move conjugated can These electrons orbitals. of set delocalized yrdzto.T epeie h p the precise, be To hybridization. nw n r tl en evl netgtd(e i.5.1). Fig. (see investigated heavily are being polythiophenes of still polyanilines, research are polypyrrols, plethora the and polyphenylenes, a known in polyfluorenes, Nowadays, diodes as boom light-emitting (OPVs). such a organic photovoltaics polymers to as, organic conductive lead such and of (OFETs), electronics discovery transistors organic This field-effect for organic [58]. ground (OLEDs), bromine the or prepared iodine and polymers with conductive reaction redox a by polymer al. nutv oyesaeacaso rai aeil htaeal ocnuteetiiy ec,these Hence, electricity. conduct to able are that materials organic of class a are polymers onductive eotdplaeyee,avr ipecnutv oye htcudb undit ihyconductive highly a into turned be could that polymer conductive simple very a polyacetylenes, reported ntemd19 mid the in xmlso odciePlmr:Shmtcrpeetto ftems omncasso odcieplmr.Psand PTs polymers. conductive of classes common most the of representation Schematic Polymers: Conductive of Examples e.g.

* Polyfluorenes rS.Plaiie h rtrpre odcieplmr a eotdb Henry by reported was polymer, conductive reported first the Polyaniline, S). or N th (59) etr,a edsrbdoiie oynlnst hwade leclr whereas color, blue deep a show to polyanilines oxidized described he as century, * Polypyrrole n N H * (62) N H z * obtl ftecro akoecmiet omamolecule-wide a form to combine backbone carbon the of -orbitals A N H * n A N H Polyaniline 46 (60) H N 3 hbiiain hc os’ euti electrical in result doesn’t which -hybridization, N H * Polythiopehene n * S (63) S Polyphenylene * * n (61) n * Shirakawa e.g. et. 2 - Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. Kumada 5.3: Figure the on dependent [61].) vastly system the is the of PTs in 3-substituted 3-position thiophenes of in 3-substituted ( of performance chains chains regioselectivity However, side side introducing the 5.3. by of solved Fig. regioselectivity be in easily shown as can thiophenes problem This processability. ensure reagents. 5.2: Figure research, polymer conductive of pioneers PT Polythiophenes 5.2 eed atyo h yeo aaytepoe ntesnhss hc swyepcal dbsdcatalysts, Pd-based especially why is which synthesis, the Pd(PPh in as employed such catalyst of type the on vastly depends h rsneo ea uha no g ait fsc ehd r hw nFg ..Temethods The 5.2. Fig. is [58]. in that reaction shown intermediate homo-coupling are metalorganic a methods a in such into product of transformed desired variety the is A towards that reacted precursor Mg. subsequently halide-based or a in Zn feature monomers as below two such shown between metal PTs polycondensations a of organometallic of Preparation involve presence backbone methods the [60]. polymer Conventional [59] the chapter. sensors twisting this molecular of in result as a attractive is achieved PTs and be conductivity makes their mechanism can and This and same color properties the conjugation. in optical by disrupting Changes their explained and be as materials. can well of polymers class as the interesting oxidation, of an upon PTs conductive make become behavior to stimuli-responsive ability the Both, 2000. r ls fplmr,ta eoecnutv pnoiain T andalto neetatrthe after interest of lot a gained PTs oxidation. upon conductive become that polymers, of class a are s ipePs ssoni i.52 r lotislbe ec,seilPshv ob rprdto prepared be to have PTs special Hence, insoluble. almost are 5.2, Fig. in shown as PTs, Simple h ytee etrdi i.53fcltt h rprto fhgl eirglrPs Regioregularity PTs. regioregular highly of preparation the facilitate 5.3 Fig. in featured syntheses The tl opigplmrzto eotdby reported polymerization coupling style - Br R 6)(67) (66) -usiue oyhohns ea-sitdsnhsso oyhohnswt eirglr3-substitutes. regioregular with polythiophenes of synthesis Metal-assisted Polythiophenes: 3-Substituted (69) R S ovninlPltipeeSnhss raoealcplcnesto f25dhl-hohnsuiiigmetal- utilizing 2,5-dihalo-thiophenes of polycondensation Organometallic Synthesis: Polythiophene Conventional S Br 3 via ) 4 NBS, AcOH/CHCl Zn*/THF, -78°C r rwe pna hyrsl nrgoadmPs[2.Sd-hi ucinlzto of functionalization Side-chain [62]. PTs regiorandom in result they as upon frowned are , lcrceia n hmclmtos oee,ol hmclmtosaereviewed are methods chemical only However, methods. chemical and electrochemical Hal Br Br 3 (64) (64) (65) S S S e.g. BrZn Br Br Br Hal R h pia ada eed infiatyo h mutadthe and amount the on significantly depends bandgap optical the 7)(70) (70) S Mccullough R S Macdiarmid M =Pd,Ni,… M(acac) Mg, THF, Ni(bipy) Mg, THF, M =Pd,Ni,Co [M] catalyst Mg orZn 2) MgBr 1) LDA/THF/-40°C -5 to25°C 4) 0,5-1mol%Ni(dppp)Cl 3) -40°Cto-5 Br 2 2 Cl . 2 2 B) *OEt Br , hw h icbsdplmrzto eotdby reported polymerization zinc-based the shows Shirakawa 2 R /-60 °Cto-40 S ZnBr HPE .GNRLBACKGROUND GENERAL 5. CHAPTER 2 Ni(dppf)Cl and

* * Heeger (63) R S 2 S n * (68) eevdaNblpiein prize Nobel a received S R * n * R S (68) Rieke S A) R hw the shows n * . 47 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ihEO n hnplmrzn ti ouino oimpruft n ercslae[63]. sulfate ferric and persulfate sodium PSS of of solution solution aqueous a an in preparing it by polymerizing achieved then be can and systems EDOT such with of Preparation charge. negative the ntepeaainof preparation the in substitution. tosyl-activated a through ether cyclic the of formation the by followed system butadiene 5.5: Figure 5.5 Fig. in shown procedure 2-step a in prepared the be require can them EDOT of all [64]. A place. However, dimethoxybutadiene ( PEDOT. first form. from of oxidized the (PSS) starting preparation its in sulfonate the in EDOT facilitate transparent polystyrene of that completely with preparation reported is are copolymerizates it methods as as of interesting especially variety especially is OPVs, PEDOT heavily in [63]). been PEDOT:PSS use has which its PTs, for of representative investigated well-known a is (PEDOT) Poly(3,4-ethylenedioxythiophene) Poly(3,4-ethylenedioxythiophene) 5.3 conductivity. 5.4: Figure bromine 5.4). or iodine (Fig. tunable as system such towards the halides approach with used, of simple doping oxidation are by a in conductive groups indicating made results be functional altered which can PTs be non-aliphatic earlier, can if mentioned As system Furthermore, the systems. of polymer. properties the electrochemical of the performance overall the affects PT eut nhge ouiiyadteeoebte rcsaiiy oee,tedge ffunctionalization of degree the However, processability. better therefore and solubility higher in results s EO tefi oryslbe oee,ti rbe scruvne ytePSmti hti used is that matrix PSS the by circumvented is problem this However, soluble. poorly is itself PEDOT ytei fEO:Peaaino DT h rtse etrsa lcrpii nrdcino h ufrao noa into atom sulfur the of introduction electrophilic an features step first The EDOT. of Preparation EDOT: of Synthesis oigo oyhohns ceai ersnaino aiedpn nue xdto fpltipee ofacilitate to polythiophenes of oxidation induced halide-doping of representation Schematic Polythiophenes: of Doping MeO e.g. 7)(73) (72) OMe Ps nti ytm EO are h oiiecag,weesPScarries PSS whereas charge, positive the carries PEDOT system, this In OPVs. SCl hexane S S 2, NaOAc, S S S S rBr Br OOH HO S S (71) (63) S doping Br S S 2 n toluene, 95°C (CH S S HPE .GNRLBACKGROUND GENERAL 5. CHAPTER 2 OH) S S 2, TsOH, S S O EDOT (74) S O e.g. 48 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ae tyee34doyhohn EO)twrsisplmrcfr poly-3,4-ethylenedioxythiophene – form polymeric Interestingly, (PEDOT). its 2003, towards In (EDOT) ethylene-3,4-dioxythiophene solvents. of nated amounts larger or solvents toxic iue6.2: Figure were systems complex more failed, the tests whether initial see these to As screened SSP. thiophene. were enable of dibromothiophenes to type solubility/processability simple designed any improve of for to variety applicable tunability a is ensure Initially, procedure to incorporated. means be a to addition, had In crystallinity. retaining while PTs. 6.1: Figure only often is polymers such of processing However, means. chemical by possible tunability extensive for allow and PT Motivation and Aims 6 Chapter hi egho h residuals. the of length chain perfor- higher in results also but greener, only not materials. procedure mance this making systems, amorphous conventional, r n ftems eerhdtpso odcieplmr speusr r fe edl available readily often are precursors as polymers conductive of types researched most the of one are s h i fti rjc a osnhsz ait fdffrn hohn rcrossial o SSP for suitable precursors thiophene different of variety a synthesize to was project this of aim The via ytei fPDT S f25dboo34ehlndoyhoee teeae eprtrsrsligi crystalline in resulting temperatures elevated at 2,5-dibromo-3,4-ethylenedioxythiopehen of SSP PEDOT: of Synthesis ytei fFntoaie Polythiophenes Functionalized of Synthesis ouinpoesn,wihrqie h oyest ehgl oul oaoduigee more even using avoid to soluble highly be to polymers the requires which solution-processing, Br O Wudl’s S O (77) S rcdr eut ncytliePswt ihrcnutvt oprdto compared conductivity higher with PTs crystalline in results procedure R O Br DBEDOT S O O 7)(76) (75) O S Br Br via 60 °Cor80 S:Plmrzto ffntnlzdpltipee etrn different featuring polythiophenes functinalized of Polymerization SSP: SSP 49 SSP Wudl n owresrpre 6]teSPo bromi- of SSP the [65] reported co-workers and O O PEDOT * S O S n O (78) S R O S O n * Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. orato curda all. at occurred reaction no uigterato.DTad3DTdd’ hwaycag napaac and appearance in change any thiosulfate show formed didn’t bromine sodium that 3MDBT the indicating and Furthermore, precipitate, DBT white a yellowish. reaction. of to formation the off-white the during showed from flask color gas-washing the in in change solution ample an showed DBBT S a efre sn cln akatce oagswsigfls.Tefls a hre ihthe with 120 charged and was 80 flask between The temperatures flask. gas-washing to a heated to then attached flask and Schlenk precursors a using performed was SSP Polymerization Solid-State 7.1.1 HTS. and SSP 7.1: Figure of feasability the test to order In Tests Initial 7.1 Discussion and Results 7 Chapter ytmmkn tcnutv,rsligi ursetproduct. fluorescent a in resulting resulted can conductive, that it changes reaction making These the system during structure. change. formed crystal was no and bromine to nature of little chemical amount in showed some change reaction that a fact the in the after to DBBT accouted of be however PXRD field. higher towards iud,wihwudo orentrsl naSP oee tsilwr sapofo ocp concerning concept of HTP proof and a possible. SSP as was both work polymerization precursors, whether these still on see it Based to However attempted SSP. solution. was in a dibromothiophenes in simple result of not polymerization the course of would which liquids, r o bet eitiueeeto est ihtesm aeadaecnetoal sdt prepare to used conventionally are and ease same however, the systems, with other a density The for electron electron suitable an density. redistribute precursors features electron to DBEDOT overall able systems of found. its not these be are influences are Comparing can thiophenes greatly environment groups. that chemical 3-functionalized functional their dioxy-system, certain Especially, in stabilizing choosing difference by large chosen. tuned a DBEDOT, were be to can 7.1) properties their (Fig. as interest, dibromothiophenes of variety a h eusae rmn utemr ce sadpn,adoiie oeaon ftethiophene the of amount some oxidized and dopant, a as acted furthermore bromine sequestated The irmtipee:DEO n ait fsml n edl vial ,-irmtipee o hi feasibility their for 2,5-dibromothiophenes available readily and simple of variety a and DBEDOT Dibromothiophenes: Br DBEDOT O O Suzuki 7)(3 7)(80) (79) (63) (75) S 1 -M fDB hwdol io hne n oesgaswr shifted were signals some and changes minor only showed DBBT of H-NMR Br tp or -type Wudl’s Br Kumada DBT S rcdr o ipeadraiyaalbetipeesystems thiophene available readily and simple for procedure Br tp oyeiain utemr,DTad3DTare 3MDBT and DBT Furthermore, polymerization. -type 50 Br 3MDBT S Br Br ◦ C o pt as uigti time, this During days. 3 to up for S DBBT S Br 1 -M eeldthat revealed H-NMR Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. rmn xlisdffrne ntediffractograms. the in differences explains bromine iue7.2: Figure SSP n T fDB:SPadHPo DBBT of HTP and SSP DBBT: of HTP and 5 5 NSTR, SSP, SSP, NSTR, NSTR, 01 02 03 04 05 60 55 50 45 40 35 30 25 20 15 10 01 02 03 04 05 60 55 50 45 40 35 30 25 20 15 10 t t R R = 24h,90°C = 24h,90°C,stirred t t t R R R = 8h,120°C = 4h,90°C = 12h,80°C 2 θ Cu-K C (80) oplmrzto cue ne ohcniin.Eiiainof Elimination conditions. both under occured polymerization No . α HPE .RSLSADDISCUSSION AND RESULTS 7. CHAPTER [°] 51 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. fe vlaigteiiilrsls twsqieaprn,ta h rcdr rpsdby proposed procedure the that apparent, quite was it results, initial the Results evaluating Initial After the of Evaluation the findings. Hence, these confirm occured. 7.1.3 7.2) SSP attempted (Fig. the samples these for of as PXRD effect, same retained. mostly the was that precursor revealed samples temperature low the a ihryloiho htihdpnigo hte oimhouft a rsn rnt niaigthat, nor indicating not, GCMS or Neither present phase separated. was aqueous sodiumthiosulfate was The whether bromine on indeed occured. depending polymerization whiteish or of yellowish instead either carbonization was that indicating obtained, was material T os’ emt esial o h oyeiaino rmntdtipee,a hs ytm emto seem systems these that as thiophenes, found, brominated 150 we of above polymerization Furthermore, temperatures the at for structure/functionality. suitable carbonize be molecular to certain seem doesn’t a HTP featuring systems for applicable T a tepe ne h aecniin stecrepnigSP utemr,eprmnsat experiments Furthermore, SSP. corresponding the as conditions same the 200 under attempted was HTP backbone. thiophene Polymerization the on Hydrothermal CH the to corresponding 7.1.2 duplets Two ppm. 3.33 at peak Water ppm. 2.5 at signal Solvent DMSO. in iha qioa muto oimhouft eumlrt h hoeia rmn otn)peet At present. content) bromine performed theoretical were the experiments to some 120 (equimolar precursor and 80 sodiumthiosulfate the between of from temperatures amount stripped be equimolar can an bromine with occurs, polymerization no if h bandpoutwsntslbei n ovninlslet.PR oee,soe eybodhalo broad very a showed however, PXRD solvents. conventional 25-27 any in around soluble not was product obtained the iue7.3: Figure ag muto rmn en omdi nauosmedium. aqueous an in formed being bromine of amount large a ...... 2.0 2.4 2.8 3.2 3.6 4.0 4.4 4.8 5.2 5.6 6.0 6.4 6.8 7.2 7.6 ◦ C eecnutd natcaewscagdwt h rcrosadwtrwsadd seven As added. was water and precursors the with charged was autoclave An conducted. were .01.92 2.00 BTNRP NMR DBBT ° (2 # Cu-K , e(lc)adPs rd h tepe S n HTP: and SSP attempted the (red) Post and (black) re α niaigta ahrta oyeiaincroiainoccurred. carbonization polymerization than rather that indicating ) ◦ C orato cue.Hwvr ntecs fte200 the of case the in However, occured. reaction no ◦ C Br nadto,aleprmnsa eprtrsaoe120 above temperatures at experiments all addition, In . S chemical shift[ppm] S Br 1 -M ol emaue o h 200 the for measured be could H-NMR HPE .RSLSADDISCUSSION AND RESULTS 7. CHAPTER 1 M pcrmo 2,2’-dibromo-5,5’-bithiophene of spectrum NMR H H 2 O DMSO ◦ C ecinablack a reaction Wudl ◦ C 1 ape,as samples, -M of H-NMR ◦ C a only was edto lead 52 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. oyei om oee,i em si nysraeplmrzto cue,a h XDsosclear shows PXRD the 27 around as black froming occured, background its polymerization amorphous towards of surface form amount only some crystalline if with white precursors as initial the seems its of it reflections from However, turned already form. product polymeric the where experiment, an oee,a 80 at however, iue7.4: Figure 80 and 60 at formed Both, radical the 7.4). that (Fig. indicates which stable air, very crystalline of Interestingly, be partially presence measured. must a the be shape reaction couldn’t by only crystallite NMR the affected that polymer, The be in indicates the to of PXRD black. solubility seem However, to poor doesn’t the white polymerization process. to from Successful Due the was color conditions. obtained. Polymerization in best in was retained the polymer solid. change stirred was verify crystalline a to was precursor white Ar by solution the under a The verified flasks of as be Schlenk minutes. DBEDOT in quickly 30 and yield could of air to under polymerization course up oven the an worked over both and THF in minutes attempted in NBS 60 EDOT NBS. using for of EDOT RT solution of bromination cooled at simple a by prepared to was added DBEDOT of was batch a procedure, the verify To 7.2.1 conditions. of optimal In polymerization verify and tested. addition, to dimerization was In the approach for discussed. sophisticated systems is BEDOT-terminated more thiophenes of a functionalized use failed, and precursors synthesis the thiophene chapter, simple this use to attempts initial As Systems DBEDOT Functionalized of Preparation 7.2 [65] eandudrteehs odtos ntal nylwtmeaueeprmnsa 80 at experiments low-temperature only Initially conditions. hash these under retained r nln ih"rsaln"PDTi literature. in PEDOT "crystalline" with line in are n h XDo h rdc lg efcl ihte80 appearance the The with variant. perfectly SSP align the to product compared the slower of be PXRD to the seemed and reaction the However, conducted. were ◦ C swl sthe as well as , T sa lentv to alternative an as HTP Wudl’s rpsdMcaimfrteSPo BDT ceeof Scheme DBEDOT: of SSP the for Mechanism Proposed Br ◦ O C 7)(5 8)(82) (81) (75) (75) S t h oyeiainwssgicnl atr h 80 The faster. significantly was polymerization the rcdr piiigConditions Optimizing – Procedure R O 5hus 200 hours, 15 = Br Br 2 Wudl’s Br O S ◦ O C rcdr a lotse ose hte rsalnt ol be could crystallinity whether see, to tested also was procedure Br Trato hwals fcytliiy oee,teefindings these However, crystallinity. of loss a show reaction HT Br Wudl’s O S Br O ◦ Wudl’s nta prahuigDEO a reproduced was DBEDOT using approach initial C Br O O HPE .RSLSADDISCUSSION AND RESULTS 7. CHAPTER S ape oh h ogtr S t60 at SSP long-term the Both, sample. SSP S rpsdmcaimo oyeiaino DBEDOT. of polymerization of mechanism proposed Br -Br ◦ C ◦ 2 C h ecincudb completed, be could reaction the S soni i.75 shows 7.5) Fig. in (shown SSP Br O S O O O ◦ S C niea NSTR an inside ° Br (2 # Cu-K , α 53 ). Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. iue7.5: Figure ehd n eyo h ietboiaino DTa eotdi 6] ehdAyeddamixture a yielded A Method two first [66]. in The 2-bromo-EDOT. reported desired as EDOT the of yielded bromination 7.6 direct the Fig. on in rely shown B methods and three A However, the methods of modification. further B for dimers method corresponding only the use and reactions dimerization controlled perform black. to white from crystals the of appearance ots h iiso hsmto,w rtatmtdt rpr ooboiae DT(EO)to (BEDOT) EDOT mono-brominated prepare to attempted first we method, this of limits the test To P leiaino BDT R fDEO,isSPadHP ecinpors ol efloe yacag in change a by followed be could progress Reaction HTP. and SSP its DBEDOT, of XRD DBEDOT: of olmerization Intensity [a.u.] DBEDOT SSP, NSTR, NSTR, SSP, 01 02 30 25 20 15 10 5 01 02 30 25 20 15 10 5 t t R R = 63h,60°C = 2.5h,80°C t t R R = 15h,80°C = 15h,200°C 2 θ Cu-K C α HPE .RSLSADDISCUSSION AND RESULTS 7. CHAPTER [°] 54 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. o oecnrle vrl ytei.Tognrlpoeue eyn ndffrn opigratoswere allows reactions also coupling but different system, on the not relying in does procedures used approach general moiety Two third This the synthesis. on overall moieties. depending controlled mono EDOT tunability more of terminal of a degree for feature preparation high that The the a for tri-thiophenes tested. as allow was stable well only systems prepare EDOT as functionalized to systems towards was approach EDOT goal third mono-brominated a failed, prepare systems to BEDOT substituted attempts Moieties initial EDOT the Terminal Featuring As Tri-thiophenes of Preparation 7.2.3 occurred dimerization products. a conditions, the indicating optimal purifying quickly, under while decayed even cases effect, which However, all additional fluorescence, molecules. in an high the showed showed of them substances conditions nature of UV-unstable these acidic highly All Interestingly, as dimerization. [66]. diethylamine, their product was with affects chromatography the conditioned which Column of silica polymerization 7.7). or to (Fig. oxide lead column, dimers aluminum can conditioned the basic a as using retained using be performed purification only and either could workup and upon dimerized However, substances the confirmed. be could formation product using achieved be can which DBEDOT, from bromine of elimination the on relies n C Synthesis possible. oe,ta EO rvdt ehgl ntbe stetemleeg ftkn akoto h freezer the of out flask a taking be seconds. of also within energy should species thermal it the the polymerize point, as fully this unstable, to At highly enough be was occurred. to polymerization proved and BEDOT dimerization that noted, direct as properly performed be oad oosbtttdEO ytm a netgtd ait f2sbtttd5booEDOT 2-substituted-5-bromo of approach another variety nature, A unstable its investigated. as well using was prepared as systems BEDOT, were of systems EDOT preparation substituted the mono in required towards effort the Substitution to of Due Effect the Evaluating 7.2.2 problem. main the being BEDOT 7.6: Figure workup oil the colorless to the due of the explained purification towards be species this, can brominated to yields mono Due the low of The [66]. polymerization PEDOT direct yields. to and low lead dimer conditions in method acidic BEDOT Using slightly prepare even polymerized. to as products possible the was chromatography it column upon B However, DBEDOT. and BEDOT of ui vnthough Even BuLi. O EDOT (73) S ytei fBDT ytei ceefrtesnhsso EO n BDTsatn rmEO.Dmrzto of Dimerization EDOT. from starting DBEDOT and BEDOT of synthesis the for scheme Synthetic BEDOT: of Synthesis O 1 eq.NBS,RT B) THF, AcOH, RT A) THF, 1eq.NBS, n uii togbs aiycpbeo eoigtehld,tesnhsscouldn’t synthesis the halide, the removing of capable easily base strong a is BuLi * O PEDOT Suzuki (75) S O O n * BEDOT opigratos h ytee eemntrduigG-Sand GC-MS using monitored were syntheses The reactions. coupling + S (83) if acidic upon workup O O Br S (84) O O O C) THF, 1,1eq. S n HPE .RSLSADDISCUSSION AND RESULTS 7. CHAPTER BuLi Br DBEDOT O O (74) EDOT (73) S S via 2 eq.NBS THF, O O Br ouncrmtgah a not was chromatography column 1-3 days 60 °C-80 * O PEDOT (75) S O n * 55 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. htcnaetterato n snta rnucdi h teaecmlx oee,uigtecomplex the using unsuitable. However, it complex. makes etherate that the fashion a in in pronounced reaction as the not down is slowed and directly reaction the affect can that eutn ope MgBr complex resulting ietyue n ope ihtedsrddbootipee h r-hohn ol eotie after MgBr obtained both be using could tri-thiophene attempted The was step thiophene. dibromo first desired The the with purification. coupled and used directly oyainpoe ob rbeai.Tescn prah(i.78 sbsdo a on based lithiation- a is mono 7.8) step, the first (Fig. of approach a workup second In The the However, problematic. be thiophene. to proved dibromo borylation 3-functionalized desired the with reaction aho sEO rvduscesu,a nalcss ataon fplmrwsotie.Ee after Even obtained. was polymer of amount same vast a the cases, in all systems -5 in these to as brominate cooling unsuccessful, to proved attempts EDOT Initial as problematic. fashion proved polymerization solution their thiophenes. 7.8: Figure 7.7: Figure rmterato a ob isptdimmediately. dissipated be to has reaction the from tepe.Tefis,bsdon based first, The attempted. species. substituted-5-bromo O pnboiaino hs r-hohn ytm h ihratvt swl stectltcntr of nature catalytic the as well as reactivity high the systems tri-thiophene these of bromination Upon 7)(87) (73) S O 1) 45 min 0 °C 2) MgBr 45 min eaaino DTTrial ucinlzdTipee:Snhtcshm o h rprto ffntoaie tri- functionalized of preparation the for scheme Synthetic Thiophenes: Functionalized Terminally EDOT of reparation P eaaino usiue DT rprto fsbtttdEO:Snhtcapoc oad h ytei f2- of synthesis the towards approach Synthetic EDOT: substituted of Preparation EDOT: Substituted of reparation n Br BuLi, -78°C ◦

DBEDOT C O O 2,

(74) Et Grignard uigterato,sm muto oye a bandidctn htha resulting heat that indicating obtained was polymer of amount some reaction, the during S 2 O Br 2 O *Et R= S egn sprepared is reagent R-B(OH) Pd(PPh NaOH, THF, 2 O epciey hswsdn u otehgl yrsoi aueo MgBr of nature hygroscopic highly the to due done was This respectively. O MgBr Suzuki Br 3 2 ) 4 (64) S NO opigrle nteltito-oyaino DTadsubsequent and EDOT of lithiation-borylation the on relied coupling NiCl THF 2 Br 2 (dppe) Br i n via O O NH

(85) O S 2 uimdae eaain h bandraetwas reagent obtained The metalation. mediated BuLi S O R S (88) S upon workup HPE .RSLSADDISCUSSION AND RESULTS 7. CHAPTER Cl 2 O 6]addehlte swl suigthe using as well as diethylether and [67] S O NBS, THF R O Kumada Br S O

(86) O O O S O S opigreaction. coupling (89) S R O S O Br 56 2 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. rmnto fteesses oedge fplmrzto cue hc ol o eaoddt date. to upon avoided However, be not moiety. could thiophene which middle occured the polymerization through of tunability degree for some into sta- allows systems, ensured insights as these approach polymerize these of well Taking synthetic to bromination as This precursors results. systems chosen. these reproducible the was of get of approach capability to bility demanding the impossible more as it synthetically well made a as irradiation consideration precursors, UV successful, the upon not Ini- were of solution out. reaction nature in carried the study were unstable to thiophenes the thiophenes of both monosubstituted SSP of of as variety boundaries a the synthesize push to to attempts aimed tial syntheses of variety a summary, In Outlook and Conclusion 7.3 HPE .RSLSADDISCUSSION AND RESULTS 7. CHAPTER 57 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. T Conclusion 8 Chapter mrhu loehr S faTP:M ooe atwspromdadrsle nsemicrystalline in resulted were and or performed background stability was thermal amorphous salt same an monomer the with TAPM:PMA with obtained a polymers were of samples SSP more altogether. - amorphous point that after inconsistently more sn M,atog h omto ftesl olntb vie loehr rsaln oyescudbe could polymers crystalline altogether, determined avoided as be Crystallinity, PMA. couldn’t PXRD. to changed salt to subsequently the according was obtained of precursor formation acid the the and although system PMA, the Using of speed reaction initial the by affected aaye ihHl yadn ml muto C oterato n ec nraigaiiy twas conditions It reaction conventional acidity. under increasing form hence could and species reaction salt different the the to vastly 200 of HCl amount (autoclave, under of small although a amount that elimination, small in found a The found furthermore adding was by salt. phenomenon HCl) a interesting with in an catalyzed by resulted and reported which thesis previously interesting was this aniline, conditions, its before of TAPM:PMDA and group elimination the preparation the on HT work in simple the intial conducted its Furthermore, been to polymers. had due 3D of system precursor synthesis prominent method. the solvent-free enabling most geometry overall the tetrahedral an was is TAPM SSP and these, HTP, Among of case the in solvent a as used is water polymers. functional towards polymerization friendly environmentally their ntedsrdplmr.I a on,ta sn : tihoer mnllne oyescudbe could polymers aminal-linked stoichiometry 1:1 a using that found, resulted was polymerization It conventional nor HTP polymers. neither However, desired problem. the compared the aldehydes As in solve of to polyimide. reactivity were expected increased of precursors was the type acids as the any attempted to only in was cases resulted polyimines towards conditions all polymerization conventional in result, or as a HT problematic under be polymerization to Neither proved retained. DATzs these of Polymerization required. at eie mnpeymtae,DTswr netgtdfrtersiaiiya mn rcrosfor precursors amine as TrisAPM- suitability the obtained of their be influence could for the DATzs investigated desired of obtained The were result The HTP. DATzs a structure. be aminophenylmethanes, diffraction crystal could Besides same same which the the systems, salt. of show simulated are with still morphologies align sampels different didn’t the the diffractograms that Nonetheless, indicating PXRD, precipitate. in polymers pattern and oligomers when occur ieetmrhlge eeotie.Ti a eepandb h ait fplmrzto ye that types polymerization of variety the by several explained that revealed be ( conditions samples can used the This the of under micrographs obtained. SEM were morphologies samples. different these than crystallinity less significantly h TramadhneHPsatn.A eprtrsabove temperatures As starting. HTP hence and realm HT the i hssdatwt h ytei n hrceiainof characterization and synthesis the with dealt thesis his h rtpr ftetei a ousdo h rprto n vlaino mn-ae precursors. amine-based of evaluation and preparation the on focussed was only as thesis techniques, the green of inherently part are first Both The polymerization. of means as chosen were SSP and HTP ◦ C , t R 410h,cmlctn oye ytei.Hwvr h omto em obe to seems formation the However, synthesis. polymer complicating h), 24-120 = T R 200 = ◦ C Gomberg oxs ln ahohr ntal u-T xssbfr reaching before exists sub-HTP Initially other. each along coexist ) T D via ≈ uc n estl Wrato ihol iia workup minimal only with reaction MW versatile and quick a 530 n19 n ol erpoue ne Tcniin (Pt- conditions HT under reproduced be could and 1898 in ◦ 58 C stesmlsobtained samples the as via N XD nrae till increased PXRD, and - T SSP S ( T eeoyl ae ooesand monomers based heterocycle - SSP ≈ 170 via t R T,hwvrfeaturing however HTP, ◦ C 2 ,btbehaved but h, 120 = r sd S can SSP used, are ) Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. nutbefrHPudrtesree odtos oee,afcl ytei aha oad ait of variety a towards pathway be synthetic could to facile that proved a found DATzs However, was morphologies. DATzs conditions. different different screened variety the a under resulting HTP time, for same unsuitable the at occur reactions of multitude ootiepr irmtihohns oedge fplmrzto ol eosvdee hncooling when even obseved be impossible could it polymerization making energy precursor, of the thermal degree of Some the to amount as dibromotrithiophenes. some problematic, pure polymerize be obtaine to to to enough proved was trithiophenes bromination these during of released bromination required The the realized iophene. be in could moiety systems thiophene such via tunable of a synthesis featuring The synthesized middle. were trithiophenes EDOT-terminated solubility, ytm osldsaeplmrz.Tesnhtcpoeuesol oee ervsdadotmzdfor optimized and the revised of be ability the however system. for should promising the procedure is brominating synthetic which system while The studies. the further ocurred of polymerize. polymerization reactivity solid-state high of to the degree to systems systems accounted designed some be the as can of evaluated this ability However, The be evaluated. couldn’t was SSP SSP for for precursors thiophiophene tunable of suitability ooti rsaln Intok,i ie sufficient given if networks, PI crystalline obtain to S oad oyhohns DTbsdsseswr hsnfrteivsiaina h polymerization the by as investigation reported the was EDOTs for brominated chosen of were systems EDOT-based polythiophenes. towards polymers SSP of conducted. preparation was the investigation was further thesis no this conditions of goal friendly the environmentally as under However, conditions. conventional under obtained T vrl,tegaso hstei eemti otcss twsson htHPi utbemethod suitable a is HTP that shown, was It cases. most in met were thesis this of goals the Overall, h eodpr ftetei a ocre ihtepeaaino hoeebsdmnmr n their and monomers thiopene-based of preparation the with concerned was thesis the of part second The ihainapoc n usqetN-aaye ecinwt h eie ucinlzddibromoth- functionalized desired the with reaction Ni-catalyzed subsequent and approach lithiation a ≈ -5 ◦ C niaigtehg eciiyo hs ytm n ec hi oeta o SSP. for potential their hence and systems these of reactivity high the indicating , e.g. Wudl eue opeaeDT-eie iatv oeue.Lsl,the Lastly, molecules. bioactive DATz-derived prepare to used be otcl h igs iavnaeo uhsses hi low their systems, such of disadvantage biggest the tackle To . t R twssonta ne h cendcniin a conditions screened the under that shown was It . via h rprto of preparation the HPE .CONCLUSION 8. CHAPTER Grignard EO reagents -EDOT 59 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. a sd ape eegon n one sloepweso iio igecytlsml odr.The holders. detector sample multichannel crystal X-Celerator single silicon an on 1 and powders between mA, loose recorded Bragg as under were 40 in mounted kV, patterns K/min diffraction and (MPD) 40 ground 10 diffractometer at were purpose Samples anode of multi- Cu used. rate diffraction was Pro a X-ray heating X‘Pert with Powder a PANalytical operating a at geometry software. with Brentano analyzer 4.3) nm 2.5. collected (Version Thermogravimetric 209 17 was or Proteus TG a system. data 2.0 NETZSCH Netzsch preparation (PXRD) size with with sample a spot sputtering equipped S and using by atmosphere, Q105T mm out coated Quarum nitrogen 10 carried a and - was with stubs 9 (TGA) alloy of carbon-coated 60/40 analysis distance on Au/Pd the working loaded of Typically a layer were with microscope. kV, thick samples FEI 10 v3.7. imaging, 200F or LAS Quanta to kV software a 5 Prior the with at using Optical out measured taken carried were unit. were images was z-gradient samples 300 microscope, (SEM) and DPX 125 microscopy head AVANCE M probe electron Bruker LEICA a inverse-broad Scanning a and mm on MHz) 5 performed (600 a was HD with microscopy III equipped Avance MHz) Bruker (300.13 a spectrometer MHz), (250.13 250 AVANCE Bruker n pcr eercre rm40 o60cm 600 to 4000 from recorded were spectra and imn rsa,uigOU vrin40 otaefrdt nlss eouinwsstt cm 4 - 2 to set was Resolution analysis. data for software 4.0) (version OPUS using crystal, diamond FT-IR-ATR Methods General 9.1 Part Experimental 9 Chapter 925sse n tpsz f0.0050134 of size step a and s/step 69.215 TSnl uduo assetoee E).Teoe a eta 100 at ICQ kept a was and oven column TR-5MS The m (EI)). 30 spectrometer with chromatography mass II gas Quadrupol APEX 1300 carried KAPPA (Trace Single were machine Bruker LT measurements Scientific GC-MS a Thermo on software. a out Jana2006 on and carried out Sadabs was Plus, (SC-XRD) Saint analysis using diffraction system X-ray diffractometer crystal Single s/turn. 4 etdt 300 to heated noted. pcr eercre naBue esr2 okn nARMcoouigMP Lwt a with QL MVP- MicroFocusing ATR in working 27 Tensor Bruker a on recorded were spectra ◦ C tart f30 of rate a at ◦ C e iue h / ai ftepa ihtehgetitniywas intensity highest the with peak the of ratio m/z The minute. per ° Å n 30 and apehlesweerttddrn h esrmn with measurement the during rotated where holders sample , − 1 . ° 60 1 and H (2 # (Cu-k 13 ouinNRsetawr eoddo a on recorded were spectra NMR solution C α ) swl s5 as well as )), ◦ C o iue n a then was and minutes 4 for ° n 60 and ° (2 # (Cu-k α )with )) − 1 , Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ufrcai vrtecus f1hu.Iomlirt a added was Isoamylnitrite hour. 1 of course the over acid sulfuric ro ne n eu odne tahdt ube a uhdwt ro n hre ihthe with charged and argon with -10 flushed to was cooled bubbler was solution a The to DMF. and attached 1 condenser step of reflux product a and inlet argon 2: Step pressure. antcsirrwscagdwt h ffwiepwe NHladmtao.Teslto a etdto heated was a solution and The condenser methanol. reflux removed and a HCl with then 2N equipped was powder flask solid off-white Another The the pistil. 90 with temperature. and charged room mortar was a to stirrer using cooling magnetic crushed after and solid flask white the tarnished from a obtain to minutes h bando-ht odrwsmle ihamra n itladwsdida 80 at dried was and pistil and mortar a with milled was powder off-white obtained The n rsl itle nln.Tefls a lwyhae o190 to heated slowly was flask chlorotriphenylmethane with The charged and aniline. argon with distilled flushed freshly was inlet and argon an to attached condenser reflux 1 Step rprto fTetraphenylmethane of Preparation TAPM of Synthesis use. before 9.2.2 acetic distilled were and DMF (>99%) and acid Aniline nitric Chlorot- university. fuming the (>99%), acid Aldrich. from acid sulphuric Sigma purchased acetic (>97%), were from glacial acid anhydride DMF, purchased hydrochloric (50%), were THF, acid acetone, PMA hypophosphinic methanol, and (>98%), aniline, PMDA 98%), TCI. ABCR. (Aldrich, from from riphenylmethane purchased purchased were was (>98%) (10%) acid mellitic Pd/C (>97%), tris(4-aminophenyl)methane (>95%), Isoamylnitrite Chemicals 9.2.1 Polyimides 9.2 M - - - - - eq. 1.75 eq. DMF 2.50 50% acid hypophosphinic isoamylnitrite acid sulphuric conc. methanol HCl 2M eq. 1.00 aniline chlorotriphenylmethane Entry ◦ C o oratrwihteslto a oldt omtmeaue lee n ahdwt water. with washed and filtered temperature, room to cooled was solution the which after hour 1 for he-ekfls qipdwt ehncsirr rsueeulzn rpigfne,ada and funnel, dropping equalizing pressure a stirrer, mechanic a with equipped flask three-neck A : he-ekfls qipdwt ehncsirr rsueeulzn rpigfne,an funnel, dropping equalizing pressure a stirrer, mechanic a with equipped flask three-neck A iue9.1 Figure ◦ C sn niesl oln ahbfr adding before bath cooling ice/salt an using via rpigfne ttesm temperature same the at funnel dropping HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER ◦ C n eta h eprtr o 15 for temperature the at kept and ◦ C ne reduced under 61 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. cd ehnladcildTFt il no-ht oi htwsdidudrvcu t80 at vacuum under acetic dried and was acid that acetic solid off-white glacial an of yield solution to NO a THF minimize adding chilled to and before hour methanol hour acid, 1 1 of for course stirred the was anhydride over portions solution small The in formation. added was tetraphenylmethane reached, was unlwscagdwt uignti cdadcoe o-15 to cooled and acid dropping nitric equalizing pressure fuming a and with condenser charged reflux a was and stirrer funnel magnetic a with equipped flask three-neck A vrtecus f3 iue n h bandslto ssirdfr1hu.Hdohshru cdwas acid Hydrophosphorous hour. 1 for stirred as solution obtained the and added minutes slowly 30 of course the over rprto fTetra-(4-nitrophenyl)methane of Preparation h uepoutwt 0%yield. % 60 with product pure the n usqetywse ihDF ae n tao wc.Teotie ht oyloihpwe was powder yellowish to white obtained The twice. 80 ethanol at and dried water DMF, with washed subsequently and eoe,adtesseso a etdt 50 to heated was suspension the and removed, ctcahdie60eq. 6.0 eq. 20.0 anhydride eq. acetic 40.0 acid acetic glacial acid nitric eq. fuming 1.00 tetraphenylmethane Entry CS(0e) / %:301(35 M+ (93,5) 320,1 (%): m/z eV): (70 GCMS il:6 fter,o-elws powder off-yellowish theory, 1 of % 60 yield: il:9 fter,wieyloihpowder white-yellowish theory, 1 of % 95 yield: M 20Mz DMSO-d6): MHz, (250 NMR H M 20Mz Chloroform-d:) MHz, (250 NMR H via ◦ C via rpigfne.Atr3 iue,teslto a lee n ahdwt lca acetic glacial with washed and filtered was solution the minutes, 30 After funnel. dropping ne eue pressure. reduced under rpigfne n H and funnel dropping δ .3(,8) .1(,8H). (d, 7.61 8H), (d, 8.23 2 δ vlto ol eosre.Atrcmlt diin oln was cooling addition, complete After observed. be could evolution .7–71 m 20H). (m, 7.16 – 7.37 ◦ C iue9.2 Figure ilhdoe vlto esd h ouinwsfiltered was solution The ceased. evolution hydrogen till ◦ C iha c/atbt.Atrtemperature After bath. ice/salt an with HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER ◦ C oobtain to 62 x Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ie ihhdoe.Teatcaewscagdwt 03 a yrgnpesr n h suspension the and pressure checked hydrogen was bar flushed conversion 20-30 being Full with before charged minutes overnight. was 5 autoclave stirred for The was argon hydrogen. with degassed with was and times Pd/C suspension 3 tetra-(4-nitrophenyl)methane, resulting with The charged was methanol. stirrer magnetic degassed a with equipped vial autoclave An eiewt H sspotn ovn.Tesletwsrmvdudrrdcdpesr n h product the and pressure reduced 80 under at removed vacuum) (fine was pressure solvent reduced The under solvent. dried was supporting as THF with Celite rprto fTetra-(4-aminophenyl)methane of Preparation ehnl- w% 0.05 methanol % 10 eq. Pd/C 1.00 tetra-(4-nitrophenyl)methane Entry il:9 fter,wiepowder white theory, 1 of % 95 yield: M 20Mz DMSO-d6): MHz, (250 NMR H δ .8–65 m H,64 .0(,8) .4(,8H). (s, 4.84 8H), (m, 6.30 – 6.47 8H), (m, 6.59 – 6.78 iue9.3 Figure via ◦ C oyeda ffwiepowder. off-white an yield to L n h ouinwsfitrdoe a of pad a over filtered was solution the and TLC HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER 63 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. a eoe rmteoe n lwycoe oro eprtr.Teotie rcptt a filtered, 80 was at precipitate pressure obtained reduced The at drying temperature. before room THF to and cooled acetone slowly water, and with washed oven the from removed was ercaon fprmlii cdadwtrwsadd h bandsseso a etdt 6 – 160 to heated was suspension obtained The added. stoichio- was a water tetrakis-(4-aminophenyl)methane, and with acid charged 180 pyromellitic was of vial amount autoclave an metric experiment, general a In to heated was suspension obtained The added. stoichio- was a water tetrakis-(4-aminophenyl)methane, and with dianhydride charged 200 pyromellitic was of vial amount autoclave an metric experiment, general a In h vnadsol oldt omtmeaue h bandpeiiaewsfitrd ahdwt water with washed filtered, was precipitate obtained The temperature. room to cooled slowly and oven the .. ytei fTP–bsdOgncPolymers polymerization Organic TAPM:PMDA based Hydrothermal TAPM– of Synthesis 9.2.3 yrtemlTP:M Polymerization TAPM:PMA Hydrothermal ae - eq. 2.00 water eq. PMA 1.00 tetra-(4-aminophenyl)methane Entry - eq. 2.00 - water eq. PMDA 1.00 tetra-(4-aminophenyl)methane Entry H H 2 2 N N ◦ ◦ C C ne uoeospesr.Atrapeeemndpro ftm,teatcaewsrmvdfrom removed was autoclave the time, of period predetermined a After pressure. autogenous under (230 TAPM TAPM (45) (45) NH NH NH NH ◦ 2 2 2 2 C 250 , NH NH ◦ 2 2 C + + ne uoeospesr.Atrapeeemndpro ftm,teautoclave the time, of period predetermined a After pressure. autogenous under ) HOOC HOOC O O O PMDA (46) PMA (90) O O O COOH COOH H H 180 -250°C 180 -250°C 2 2 O, O, iue9.4 Figure iue9.5 Figure N N HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER N N N N N N O O O O ◦ C TAPM-PI TAPM-PI (47) (47) o tlat2 hours. 24 least at for O O O O N N N N N N N N 64 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. a eoe rmteoe n lwycoe oro eprtr.Teotie rcptt a filtered, 80 was at precipitate pressure obtained reduced The at drying temperature. before room THF to and cooled acetone slowly water, and with washed oven the from removed was tihoercaon fprmlii cdadwtrwsadd h upninwsdgse o 15 for degassed was suspension The tetrakis-(4-aminophenyl)methane, added. with was with water charged and was acid flask pyromellitic of bottom amount round stoichiometric a a experiment, general a IIn to heated was suspension obtained The added. was water stoichio- and a (PMA) tetrakis-(4-aminophenyl)-methane, with acid 200 charged pyromellitic was of vial amount autoclave metric an experiment, general a In ytei fTrisAPM-carbocation of amount. Synthesis required the in obtained be not could product the eoedyn trdcdpesr t80 at pressure reduced at drying before ytei fteTP:M ooe Salt Monomer TAPM:PMA the of Synthesis in measured. obtained was was product SC-XRD desired The needles. crystalline product. main green the as as amounts obtained small was PMA with TAPM of polymerization H ae - eq. 2.00 water eq. PMA 1.00 tetra-(4-aminophenyl)methane Entry - eq. 2.00 water eq. PMA 1.00 tetra-(4-aminophenyl)methane Entry 2 N ◦ C (230 H TAPM 2 (45) NH NH N 2 2 ◦ C 250 , TAPM (45) NH NH NH 2 2 2 ◦ C + ne uoeospesr.Atrapeeemndpro ftm,teautoclave the time, of period predetermined a After pressure. autogenous under ) HOOC HOOC NH 2 PMA (90) + HOOC HOOC COOH COOH PMA (90) ◦ H RT C 2 O, COOH COOH o tlat2 or.Aprl rcptt eutn rmthe from resulting precipitate purple A hours. 24 least at for iue9.6 Figure iue9.7 Figure H 160 -180°C 2 O, HOOC OOC H 2 COO COOH N Monomer Salt HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER H (92) 3 NH N 1 -M ol o emaue as measured be not could H-NMR TrisAPM-carbocation 2 NH (91) ◦ NH NH C 2 3 3 o tlat2 hours. 24 least at for HOOC OOC NH 3 HOOC OOC COOH COOH COO COOH 65 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. nagnrleprmn,aShekfls a hre ihteTP:M-mnmrsl.Vcu between Vacuum salt. monomer TAPM:PMA- the 10 with and charged was mbar flask 10 Schlenk a experiment, general a In HOOC acetone of amounts small and solution water temperature. looking room with brownish at washed initially pressure and reduced the under filtered hour, samples was 1 the product After drying obtained before The temperature. room lighter. at turned overnight stirred and minutes rhae i ahfra es 4adu o7 or.Atrcoigt omtmeaue h precipitate the temperature, room to cooling After hours. 72 to up and 24 least collected. at was for bath oil preheated oi-tt oyeiaino h ooe Salt Monomer the of Polymerization Solid-State OOC ooe at10 eq. 1.00 Salt Monomer Entry il:9 fter,o-ht powder off-white theory, 1 of % 95 yield: M 60Mz DMSO-d6): MHz, (600 NMR H COO COOH Monomer Salt H (92) 3 − N 3 brwsapidfr1 iue eoetefls a etdt 0 200 - 100 to heated was flask the before minutes 10 for applied was mbar NH NH 3 3 NH 3 HOOC OOC δ .9(,4) .8–67 m H,65 .1(,8H). (m, 6.51 – 6.59 8H), (m, 6.74 – 6.78 4H), (s, 8.09 COO COOH iue9.8 Figure SSP, 100-200°C N HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER N N N O O TAPM-PI (47) O O N N N ◦ C na in 66 N Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. muto yoeltcdahdieadwtrwsadd h bandsseso a etdt 200 to heated was suspension obtained The added. stoichiometric was a tris(4-aminophenyl)methane, water with and charged dianhydride was ◦ pyromellitic vial of autoclave an amount experiment, general a In ihwtr ctn n H eoedyn trdcdpesr t80 at pressure washed reduced filtered, at was drying precipitate before obtained The THF and temperature. room acetone to water, cooled with slowly and oven the from removed yrtemlPlmrzto fTrisAPM:PMDA of Polymerization Hydrothermal C ae - eq. 2.00 water eq. PMDA 1.00 tris-(4-aminophenyl)methane Entry H (230 2 N ◦ C 250 , TrisAPM (49) NH 2 ◦ C ne uoeospesr.Atrapeeemndpro ftm,teatcaewas autoclave the time, of period predetermined a After pressure. autogenous under ) NH + 2 O O O PMDA (46) O O O H 180 -250°C 2 O iue9.9 Figure N N HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER ◦ C o tlat2 hours. 24 least at for N O O TrisAPM-PI (47) O O N N N 67 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. muto eltcai MlA n ae a de.Teotie upninwshae o200 to heated was suspension obtained The stoichiometric added. a was water tris(4-aminophenyl)-methane, and with (MellA) charged acid was mellitic vial of autoclave amount an experiment, general a In rmteoe n lwycoe oro eprtr.Teotie rcptt a lee,wse with washed filtered, 80 was at precipitate pressure obtained reduced The at drying temperature. before room THF to and cooled acetone slowly water, and oven the from yrtemlPlmrzto fTrisAPM:MellA of Polymerization Hydrothermal ◦ C ae - eq. 1.00 water eq. MellA 1.00 tris-(4-aminophenyl)methane Entry 250 , H 2 N ◦ C ne uoeospesr.Atrapeeemndpro ftm,teatcaewsremoved was autoclave the time, of period predetermined a After pressure. autogenous under ) TrisAPM (49) NH 2 NH 2 + HOOC HOOC MellA (51) COOH COOH COOH COOH iue9.10 Figure H 180 -250°C 2 O, ◦ C N HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER o tlat2 hours. 24 least at for N N O N O O N O O N O N TrisAPM:Mell-PI N (93) ◦ C N (230 68 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. rcros oasu yrxd n -ehxehnl h ilwsflse ihagnadhae o190 to heated desired and the argon with with all charged flushed and was was vial precursor vial microwave the The mL of 20 2-methoxyethanol. ◦ environment a and procedure, hydroxide chemical diamino- general potassium the desired a precursors, the according In yield slightly below. to tuned reported dicyanamide are be with syntheses to cyanide had a Conditions of cyclotrimerization triazine. a is reaction described The diaminotriazines of Synthesis General 9.3.2 and dried were uni- mesitylene the and use. dioxane from before n-propanol, distilled purchased o-dichlorobenzene, ethanol, were toluene, NMP, (99%) o-dichlorobenzene, DMSO, THF, terephthalaldehyde toluene, and versity. NMP, mesitylene DMSO, dioxane, THF, n-propanol, acetone, ethylacetate, 3-cyanobenzaldehyde methanol, 4-cyanopyridine, 4-nitrophenylbenzonitrile hydroxide, 4-aminobenzonitrile, KOH, sodium (99%), (99%), paraffine dichlorodiethylether, in Imidazole dihydrate, suspension tinchloride TCI. (60% 2-Methoxyethanol oil), hydride from sodium purchased Aldrich. (>90%), was Sigma 1,4-diamino-2,3-dicyano-9,10-anthraquinone (>97%), >99%) from BHT, purchased with was (stabilized (98%) 1,4-dicyanobenzene (99%), Dicyandiamide Chemicals 9.3.1 Diaminotriazines 9.3 ytei fBs(,-imn-,,-raie-ezn (BATB) Bis-(2,4-diamino-1,3,5-triazine)-benzene of Synthesis purified. C o o1 i namcoae h ilwscoe oro eprtr n h bandproduct obtained the and temperature room to cooled was vial The microwave. a in min 10 to 5 for (52) R =CN,NO R CN Methoxyethanol Dicyandiamide, KOH MW, 190°C 2, COOH H OH 2 N iue9.12 Figure 9.11 Figure NH N H CN N R via cyclotrimerization HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER H 2 N N N DATz (53) R N NH 2 69 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. h ouinwscoe oro eprtr n h bandpeiiaewsfitrd ahdtiewith twice pressure. reduced washed under filtered, dried was was precipitate product obtained orange the The and acetone. temperature and room methanol to cooled was solution The lee,adteotie rcptt a ahdtiewt ehnladaeoe h ffwieproduct was off-white solution The The acetone. and dicyanobenzene. methanol with pressure. 1,4- and twice reduced and water under washed hot dicyandiamide dried was onto was precipitate remaining poured obtained remove was the precipitate to and obtained filtered, minutes the and 10 temperature for room stirred to cooled was solution The ytei f6Ntohnl24daio135tizn (4-NO 6-Nitrophenyl-2,4-diamino-1,3,5-triazine of Synthesis -ehxehnl10.00 [mL] 0.102 V 0.019 [g] m 1.77 0.34 [mmol] 0.151 n 1.73 0.34 2-methoxyethanol eq. 1.02 hydroxide potassium 1.00 dicyandiamide 4-nitrobenzonitrile compound -ehxehnl14.00 [mL] V 1.008 0.112 [g] m 12.00 2.00 [mmol] n 0.768 2.00 0.18 2-methoxyethanol eq. 6.00 hydroxide potassium dicyandiamide 1.00 1,4-dicyanobenzene compound il:012g(0%o hoy,oag precipitate orange theory), of % 1 (60 g 0,142 yield: il:14 7, fter) ffwie rsaln solid crystalline off-white, theory), of % 1 (79,9 g 1,42 yield: M 20Mz DMSO-d6): MHz, (250 NMR H M 20Mz DMSO-d6): MHz, (250 NMR H δ δ .1–84 m H,83 .1(,2) .4(,4H). (s, 6.94 2H), (m, 8.31 – 8.39 2H), (m, 8.42 – 8.51 .2(,4) .7(,8H). (s, 6.77 4H), (s, 8.32 iue9.13 Figure 2 PhTz) HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER 70 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ytei f4(,-Daio135tizn2y) ezi acid benzoic Diamino-1,3,5-triazin-2-yl)- 4-(4,6- of Synthesis precursor the mostly of mixture a revealed and formed. removed was product quenching upon solvent little precipitate The with a in isopropanol. result or didn’t acetone that obtained water, was with solution yellow a reaction, microwave the After ihwtr ctn riorpnl h ouinwsrdcdt rns n eeldamxueo mostly of mixture a revealed and dryness to formed. reduced product was little solution with quenching upon The precursor precipitate the a isopropanol. in or result didn’t acetone that water, obtained was with solution yellow a reaction, microwave the After ytei f6Aiohnl24daio135tizn (4-NH 6-Aminophenyl-2,4-diamino-1,3,5-triazine of Synthesis -ehxehnl6.00 [mL] 0.104 V 0.017 [g] m 1.30 0.30 [mmol] 0.118 n 1.30 0.30 2-methoxyethanol eq. 1.00 hydroxide potassium 1.00 dicyandiamide 4-nitrobenzonitrile compound -ehxehnl6.00 [mL] 0.084 V 0.059 [g] m 1.00 1.05 [mmol] 0.118 n 1.30 1.05 2-methoxyethanol eq. 1.00 hydroxide potassium 1.00 dicyandiamide 4-nitrobenzonitrile compound il:0% yield: il:0% yield: H 2 iue9.14 Figure iue9.15 Figure N N N (95) NH N 2 NH 2 2 PhTz) HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER 71 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. h ouinwscoe oro eprtr n h bandpeiiaewsfitrd ahdtiewith product. twice the washed not filtered, was was precipitate precipitate off-white obtained obtained the The and acetone. temperature and room methanol to cooled was solution The etaie sn NHladtersligpeiiaefitrd ahdwt tao n re oyeda yield to dried and ethanol with was washed solution filtered, The precipitate hours. resulting 30 for the precipitate. reflux white and to dicyandiamide, HCl heated 4-cyanobenzoicacid, 2N was with solution using charged The neutralized was ethanol. condenser methoxy and reflux hydroxide a potassium with equipped flask three-neck A acid benzoic Diamino-1,3,5-triazin-2-yl)- 4-(4,6- of synthesis Alternative ytei f4(,-Daio135tizn2y) ezi aldehyde benzoic Diamino-1,3,5-triazin-2-yl)- 4-(4,6- of Synthesis -ehxehnl5.00 [mL] 0.084 V 0.008 [g] m 1.00 0.15 [mmol] 0.118 n 1.00 0.15 2-methoxyethanol eq. 1.00 hydroxide potassium 1.00 dicyandiamide 4-nitrobenzonitrile compound -ehxehnl6.00 [mL] 0.084 V 0.059 [g] m 1.00 1.05 [mmol] 0.118 n 1.30 1.05 2-methoxyethanol eq. 1.00 hydroxide potassium 1.00 dicyandiamide 4-nitrobenzonitrile compound il:0% yield: il:015g(0 fter) ht precipitate white theory), of 1 (80% g 0,185 yield: M 20Mz DMSO-d6): MHz, (250 NMR H δ .0–81 d H,79 .4(d H,67 s 4H). (s, 6.74 2H), (dd, 7.84 – 7.95 2H), (d, 8.10 – 8.20 iue9.16 Figure HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER 72 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ytei f14Daio2(,-diamino-1,3,5-triazin-2-yl)-3-dicyano-9,10-anthraquinone 1,4-Diamino-2-(4,6- of Synthesis was product The and methanol. temperature from room recrystallized to was cooled precipitate was recrystallization. obtained solution hydrothermal with The using the twice recrystallized reaction, washed subsequently removed. filtered, microwave was was the precipitate solvent After obtained the the and acetone. temperature and room methanol to cooled was solution The ytei f4(,-Daio135tizn2y) pyridine Diamino-1,3,5-triazin-2-yl)- 4-(4,6- of Synthesis lee n a ahdtiewt ehnladaeoe h rdc a banda itr fthe of mixture a as obtained was product The precipitatewas acetone. obtained product. and the monotriazine methanol and the temperature with and room twice precursor to washed cooled was was and solution filtered the reaction microwave the After -ehxehnl6.00 [mL] 0.109 V 0.019 [g] m 1.30 0.30 [mmol] 0.104 n 1.30 0.30 2-methoxyethanol eq. 1.00 hydroxide potassium 1.00 dicyandiamide 4-nitrobenzonitrile compound opude.n[ml g [mL] 0.218 V 0.017 [g] m 2.60 0.30 [mmol] n 2.60 0.30 eq. 0.288 2-methoxyethanol hydroxide 1.00 potassium dicyandiamide 1.00 1,4-diamino-2,3-dicyano-9,10-anthraquinone compound il:005g(45%o hoy,wieyloihcrystals white-yellowish theory), of % (34,5 g 0,065 yield: il:002 1,%o hoy,dr leprecipitate blue dark theory), of (15,7% 0,072g yield: iue9.17 Figure iue9.18 Figure HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER 6.00 73 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ytei f14Daio2(,-diamino-1,3,5-triazin-2-yl)-3-dicyano-9,10-anthraquinone 1,4-Diamino-2-(4,6- of Synthesis h ouinwsnurlzduig2 C n h eutn rcptt lee,wse ihehnland ethanol with washed hours. filtered, 30 precipitate precipitate. for resulting white reflux the a and to yield HCl heated to 2N was dried using solution neutralized The was solution ethanol. The methoxy and 1,4-diamino-2,3-dicyano-9,10-anthraquinone, hydroxide with charged potassium was condenser dicyandiamide, reflux a with equipped flask three-neck A opude.n[ml g [mL] 0.218 V 0.017 [g] m 2.60 0.30 [mmol] n 2.60 0.30 eq. 0.288 2-methoxyethanol hydroxide 1.00 potassium dicyandiamide 1.00 1,4-diamino-2,3-dicyano-9,10-anthraquinone compound il:030g(33 fter) akbu rcptt ooraiecompound monotriazine – precipitate blue dark theory), of 1 (83.3% g 0.310 yield: M 60Mz MOd) .7–82 m H,79 .6(,2) .4(,J=1. z 4H). Hz, 11.3 = J (d, 7.14 2H), (m, 7.86 – 7.93 2H), (m, 8.20 – 8.27 DMSO-d6): MHz, (600 NMR H HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER 6.00 74 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ls :A rflse 0m -ekfls a hre ih4-NO with charged was flask 3-neck mL 50 flushed Ar An A: Flask rprto f44-6(-irpey)135tizn24dy)dmrhln (4-NO 4,4’-(6-(4-Nitrophenyl)-1,3,5-triazin-2,4-diyl)-dimorpholine of Preparation Dimorpholinotriazines of Synthesis 9.3.3 .0–34 m 16H). (m, 3.48 – 4.30 ls :A rflse 0m -ekfls a hre ihsduhdiead37 LDFwr added. were DMF mL 65 3,75 to and heated sodiumhydride with were charged B was flask and 3-neck A mL Ar. 50 Solution under flushed stirred Ar An was B: solution Flask The added. were DMF dry ahdwt odehnl igecytl ol utemr eotie hog ertalzto nDMF. in recrytsallization through obtained be furthermore could Single-crystals ethanol. cold with washed ih rw rcptt.Teslto a lee n ahdwt tH h rcptt a re o 2 for dried was precipitate 80 The obtain at EtOH. to oven with minutes washed drying 45 and vacuum for filtered stirred a was and in solution ice hours on The poured precipitate. subsequently brown was light that a solution brown a obtain to minutes pncmiigtesltos oo meitl hne obak h ouinwssirda 60 at stirred cannula. was a solution The using B black. solution to into changed A immediately solution color transferring solutions, before the suspension combining a Upon obtain to increased further was ihooityehr21 .41231.06 1.293 9.04 0.738 2.10 18.46 4.29 DMF dispersion 60% sodiumhydroxyde dichlorodiethylether opude.n[ml g [mL] V [g] m [mmol] n eq. 4-NO compound il:08 7 fter) rnet rw odr-oag rsasatrrecrystallization. after crystals orange - powder brown to orange theory), of % 1 (77 g 0,80 yield: M 20Mz Chloroform-d): MHz, (250 NMR H 2 hz10 .11.000 4.31 1.00 PhTz ◦ C ◦ δ C eoebigrflxdi tao.Tepeiiaewsfitrdand filtered was precipitate The ethanol. in refluxed being before .5(d,J=90 .,20H,2) .9(q .,21H,2H), Hz, 2.1 9.2, = J (dq, 8.29 2H), Hz, 2.0 4.6, 9.0, = J (ddd, 8.55 oyedssesosi ohcss eprtr fslto A solution of Temperature cases. both in suspensions yield to iue9.19 Figure 8.75 HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER 2 hz ihooityehrad5mL 5 and dichlorodiethylether PhTz, 2 PhMTz) ◦ C o 90 for 75 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. 5m akwscagdwt 4-NO with charged was flask mL 25 A rprto f44-6(-mnpey)135tizn24dy)dmrhln (4-NH 4,4’-(6-(4-Aminophenyl)-1,3,5-triazin-2,4-diyl)-dimorpholine of Preparation ihagnadhae o80 to heated and argon with .6(,16H). (m, 3.56 ordot ae,adnurlzduig1NNO.Apeiiaefre fe ecignurlp which pH neutral vacuum. reaching high after under formed dried precipitate and A ethanol NaOH. with N washed 1 filtered, using was neutralized and water, onto poured SnCl opude.n[ml g [mL] V [g] m [mmol] n eq. 4-NO compound ty ctt 10.00 acetate ethyl il:009 7, ) elwpowder yellow 1 %), (70,7 0,089g yield: M 20Mz DMSO-d6): MHz, (250 NMR H 2 2 *2H PT .004 0.150 0.40 1.00 MPhTz 2 .020 0.454 2.01 5.00 O ◦ C h ouinwssirdoengtadatrcoigdw,teslto was solution the down, cooling after and overnight stirred was solution The . 2 hT,tnhoiedhdaeadehlctt.Tefls a flushed was flask The ethylacetete. and tinchloride-dihydrate PhMTz, δ .6(,J=86H,2) .2–65 m H,57 s H,39 – 3.92 2H), (s, 5.71 2H), (m, 6.51 – 6.62 2H), Hz, 8.6 = J (d, 8.06 iue9.20 Figure HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER 2 PhMTz) 76 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ovn/aaytsse.Teslto a easdwt ro n tahdt a to attached desired the and as argon well as with precursos degassed desired the was with solution charged was The flask 3-neck system. mL 50 solvent/catalyst a procedure, general a In cimti mut n ae a de.Tesse a hnhae o180-250 to heated sto- then in precursors was desired system the The with charged added. was vial was mircrowave water a and or amounts autoclave ichiometric an procedure general a In polymerization Hydrothermal Polyimides Towards Polymerizations Attempted DATz’s of Polymerizations 9.3.4 upnin eefitrd nalcss rcptt rgntn rmteDT rcro a obtained. was precursor the DATz down, the Polymerization from reactor Conventional originating the precipitate cooling a After cases, hours. all 24-72 In for filtered. reacted were were suspensions reactions autoclave the whereas minutes ecinwshae orflxfr2-6husbfr oln ont omtmeaue h solutions was The precursor DATz the temperature. from room originating to precipitate a down cases, cooling all before In hours acetone. obtained. with 24-96 washed for and filtered reflux were to heated was reaction uolvsad230 and autoclaves mdzl 72 24 24 24/48/72/96 24 - LiBr isoquinoline - - imidazole toluene DMSO/ NMP NMP NMP ovn ytmctls ecintime[h] reaction Zn(OAc) catalyst imidazole DMSO/ System Solvent ◦ C ncs ftemcoae irwv ecin eeuulycnutdfr30-180 for conducted usually were reactions Microwave microwave. the of case in 2 24 iue9.21 Figure HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER Dean ◦ C prue The aperture. ncs fthe of case in 77 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. nagnrlpoeue natcaewscagdwt h rcrosadwshae o200 to heated was and precursors the with charged was autoclave an procedure, general a In a cases, all In acetone. with Polymerization Hydrothermal washed and obtained. filtered was hours. chosen precursor were 48-72 the DATz solutions for and the reflux the from precursors to originating desired temperature, heated precipitate the room subsequently with and to charged degassed was cooling was flask After suspension neck obtained single The mL system. 10 solvent a procedure, general a In Polymerization Conventional Polyimines Towards Polymerizations Attempted 2husteatcae eecoe oro eprtr n lee.Tefitaewswse ihwater with washed was precursor. filtrate DATz The the from filtered. originated and precipitate temperature obtained room The to acetone. cooled and were autoclaves the hours 72 ae 8 72 48/ 72 48/ - AcOH 6N time[h] reaction 72 water catalyst 72 water System Solvent - - 72 72 48/ time[h] reaction catalyst 72 AcOH - 48/ toluene 6N DMSO/ DMSO AcOH n-propanol 6N o-dichlorobenzene/ n-propanol o-dichlorobenzene/ mesitylene dioxane/ System Solvent iue9.22 Figure HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER ◦ C fe 8– 48 After . 78 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ae,aeoeadTF h bandaia-ikdplmrwsdida brad50 and mbar with 6 washed at filtered, dried obtained, was was polymer precipitate aminal-linked yellow obtained to The white THF. a and temperature, acetone water, room to cooling After hours. usqetyhae o180 to heated subsequently ihagn r,fehydsildDS a de n h ouinwsdgse hl etn o100 to heating while degassed was solution the flushing and After added terephthalaldehyde. was and BATB DMSO with distilled charged freshly was ◦ flask dry, 3-neck argon, mL with 50 flushed argon and dry A Polymers Aminal-linked Towards Polymerization C AB10 .00.593 [mL] V 2.00 [g] m 1.00 0.268 [mmol] n 2.00 eq. DMSO 1.00 Terephthalaldehyde BATB compound pnrahn 100 reaching Upon . ◦ C h rcroswr isle,adbbln a tpe.Teslto was solution The stopped. was bubbling and dissolved, were precursors the ◦ C n h bandylo ouinwssirda hstmeauefr72 for temperature this at stirred was solution yellow obtained the and iue9.23 Figure 20.00 HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER ◦ C o hours. 2 for 79 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. a e ocytlieoe ih.Tepoutwsotie fe lrto swiecytlieneedels liquor crystalline mother white the with as times filtration three after repeated obtained was soltuion yield. procedure the was the washed This and product maximize were added methanol. to The were layers chilled ethanol organic with mL night. washed combined 5 onto were The over mL. which poured THF. 10 crystallize was mL to to solution 50 solution set The the with after concentrating was times temperature. yellow before three room to brine extracted at and changed and hours water but KOH with 4 blue/purple for M dark stirred 1 to was mL with changed course solution 100 charged initially the The over was color portions minute. and NBS small septum 1 in adding solution a around Upon the and to inlet minutes. added was argon 25 NBS an THF. of degassed flask, and washing flow glas arogn a under EDOT with equipped flask three-neck A T Chemicals 9.4.1 Polythiophenes 9.4 .. rprto fDEO,BDTadPEDOT 2,5-Dibromo-3,4-ethylenedioxythiopehene and of BEDOT Synthesis DBEDOT, of Preparation 9.4.2 use. before 2,5- sodium over etherate, dried magnesiumbromide was THF (98%), purchased university. were bromide (97%) the Magnesium 2-bromothiophene from and THF Aldrich. carbonate, potassium Sigma (96%), dibromo-3-n-butyl-thiophene from purchased were anes 9%,25dboohohn 9%,5clr--heybrncai and acid 5-chloro-2-thienylboronic (95%), 2,5-dibromothiophene (97%), 2,5-dibromo-3-methylthiophene (97%), acid 4-nitrophenylboronic from (99%), purchased 5,5’-Dibromo-2,2’bithiophene were ABCR. (97%) 3-bromothiophene and nickel(II)chloride 1,3-Bis(diphenylphosphino)propane TCI. ispoy oae(98%), borate riisopropyl H 30.00 0.85 2.99 1.14 16.80 [mL] 2.10 8.00 V [g] THF m 1.00 [mmol] NBS n EDOT eq. compound il:157g(4%,wiecrystals white %), 1 (64 g 1,537 yield: M 20Mz DMSO-d6): MHz, (250 NMR H N booucnmd 9% n -hoohnlooi cdwr ucae from purchased were acid 3-chlorophenylboronic and (98%) -bromosuccinimide δ .0(,4H). (s, 4.30 iue9.24 Figure HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER n btlihu ouin25 nhex- in 2,5M solution -butyllithium 80 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. n ae.Sm xeinswr utemr are u sn oimhoupaet iiieters if 200 precursors risk and the dibromothiopehene 80 minimize at desired to out the sodiumthiosulphate carried of using were mmol Reactions out 1 carried sequestated. furthermore with was were charged bromine experients was Some NSTR water. a and procedure, general a In Dibromothiophenes of Polymerization 120 Hydrothermal Attempted or 80 to heated occured. bithio- was polymerization 5-5’-Dibromo-2,2’- was no for flask thiosulphate occured however The dehalogenation phene sodium of with degree precursor. Some flask dibromothiopehene 2,5-dibromo-3-methylthiophene. washing and desired gas the a to of connected degreeCelsius mmol flask 1 Schlenk with a charged procedure, general a In Dibromothiophenes of SSP Attempted hours. 2-65 for polymerized were akwscagdwt 0m fDEO n eld h akwspae na vna 60-80 at oven an in placed was flask The sealed. and DBEDOT of mg 50 with charged was flask A ne rg o n easdTF B a de oteslto nsalprin vrtecus f25 of course the over portions small EDOT in with solution charged the was to septum added a was and NBS inlet THF. argon degassed an and flask, flow washing arogn glas under a with equipped flask three-neck A ytei f2Boo34ehlndoyhohn ehdA Method 2-Bromo-3,4-ethylenedioxythiophene of Synthesis 200 oyeiaino 2,5-Dibromo-3,4-ethylenedioxythiopehene of Polymerization BDT10 .70.05 [mL] V [g] 0.17 m [mmol] n 1.00 DBEDOT eq. compound H 15.00 0.748 0.43 4.20 0.569 [mL] V 1.05 4.00 [g] m THF 1.00 [mmol] NBS n EDOT eq. compound il:004g(0 ) lc rsaln material crystalline black %), (100 g 0,024 yield: ◦ C nteohrhn,croiainocrdfralsamples. all for occured carbonization hand, other the on n eta h eprtr o 47 or.N ecinocrdfr2,5-dibromothiophene for occured reaction No hours. 24-72 for temperature the at kept and iue9.25 Figure iue9.26 Figure HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER ◦ C t80 At . ◦ C orato cue.At occured. reaction no ◦ C and 81 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ytei f2Boo34ehlndoyhohn ehdB Method 2-Bromo-3,4-ethylenedioxythiophene of Synthesis and polymerized product the 2:5) (PE:DCM chromatography retained. column be using couldn’t purification Upon removed. was 0m he-ekfls ihaspu n ube a uhdwt ro n hre ihDBEDOT with charged and -78 argon to with flushed cooled was was bubbler solution a The and THF. septum a dry with and flask three-neck mL 50 A Ladteylo ouinwssoe ntefezr pntkn h ouinoto h ree phase a freezer the C of Method out polymerization. 2-Bromo-3,4-ethylenedioxythiophene solution indicating of the formed Synthesis 5 taking had to precipitate Upon reduced black freezer. was a the solvent and mL in The observed 50 stored be with sulphate. times was could magnesium two separation solution over extracted yellow The dried was the solution were hours. The and layers with 2 mL separation. organic extracted for phase combined was a temperature which the obtain obtained room and colorless to was at THF the added emulsion stirred be white to to a was added had and was reaction water Brine NBS the THF. onto poured and flow. was arogn minutes EDOT solution under 20 with purple acid charged of slightly was acetic course septum glacial the a and and over THF inlet solution of argon an mixture flask, degassed washing a glas and a with equipped flask three-neck A MgSO over of dried mL separated, 25 were onto layers was organic poured phase combined was organic The brine.The solution THF. The and mL 75 water around temperature. with with after room times washed yellow at three hours to extracted 4 and changed thiosulphate for but sodium stirred blue/purple saturated was dark solution to The changed minute. initially 1 color NBS adding Upon minutes. lca ctcai 10.00 0.748 0.43 4.20 0.569 [mL] V 1.05 4.00 [g] m 1.00 [mmol] n THF acid eq. acetic glacial NBS EDOT compound H 15.00 0.600 [mL] V [g] 2.00 m [mmol] THF n 1.00 n eq. DBEDOT compound BL .M11 .00.88 2.20 1.10 2.5M -BuLi ◦ iue9.27 Figure iue9.28 Figure C 15.00 sn naeoelqi irgnbt and bath nitrogen acetone/liquid an using HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER 4 lee n h solvent the and filtered , n BL was -BuLi 82 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ih ntefezraduo aigi u ftefezri oyeie immediatly. polymerized over it stored freezer was the product of The out (triethylamine it obtained. not taking phase was upon solid product and conditioned product pure freezer the basic a the that but a in reavealed 2:5) night with (PE:DCM precipitate chromatography conducted the Column was of used) NMR impure. stored was and precipitate. was over mL off-white but 30 dried a to water formed and yield concentrated mL brine was was to with 30 solution overnight The washed with it freezer were solution. quenched letting the yellow layers was before in slightly organic solution hours a combined The obtain 2 The to for hours. sulphate DCM. magnesium temperature 3 with this another times at for three extracted stirring stirred and and was temperature solution room The to minutes. warm 2 over dropwise added HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER 83 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. o1 Lad5m tao a de.Tepoutwsotie sabonolwihwsfudt ea be to product. found 2-Bromo-5-(nitrophenyl)-3,4-ethylenedioxythiophene main was of the which Synthesis as oil dimer brown corresponding a the as and obtained product was side product a The reduced as was product added. to solvent desired was The yellow the ethanol combined sulphate. of mL the magnesium mixture 5 and over and dried celite mL and over 10 brine filtered with to was washed solution were The layers organic heating. brown upon black turned solutiuon The h iudpeusr eedgse eoebigaddt h il h upninwssirda room at stirred precursors. was solid suspension the The 130 with vial. to charged heated the and being to before argon added minute with being 1 flushed before for degassed was temperature were vial precursors microwave liquid a The procedure, general a In Assisted Microwave the for Procedure systems General 2-Substituted-EDOT of Preparation 9.4.3 ytei f2-Bromo-5-(Chlorothienyl)-3,4-ethylenedioxythiophene of Synthesis oasu abnt M1.035 1.85 3.50 10.00 THF 2M carbonate potassium BDT10 .50.107 [mL] V [g] 0.35 m [mmol] n 1.00 eq. 0.058 1.00 Pd(PPh acid 5-Chlorothienylboronic DBEDOT compound il:0% yield: 3 ) 4 .500 0.046 0.04 0.05 iue9.29 Figure iue9.31 Figure 9.30 Figure Suzuki ◦ C o hour. 1 for opigreactions coupling 3.75 HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER 84 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. rn.Teognclyr eedidoe ansu upaeadtesletwsrmvd M fthe of product. NMR main removed. the and was as water obtained solvent with was the washed dimer and and the sulphate THF that magnesium revealed with over solid oil extracted black dried brown Celite, a were dark over of layers filtered formation organic the was The and solution brine. temperature The reaction reaching observed. after be obtained could was solution yellow dark A pnhaigt 130 to heating Upon n h ovn a eoe.NRo h rw rcptt eeldta h ie a bandalmost obtained was dimer the that revealed precipitate PPh brown the sulphate the from magnesium originating of over signals NMR dried Furthermore, organic were exclusively. combined removed. layers The organic was THF. combined solvent mL The the 150 brine. with and and washed water and with Celite washed over were filtered layers was suspension dark obtained The ytei f2-Bromo-5-(aminonitrophenyl)-3,4-ethylenedioxythiophene of Synthesis catalyst. the for harsh too were oasu abnt .037 0.518 3.75 5.00 THF carbonate potassium oasu abnt M1.035 3.75 3.50 10.00 DMF 2M carbonate potassium BDT10 .50.225 [mL] V [g] 0.75 m [mmol] n 1.00 eq. 0.164 0.75 Pd(PPh 1.00 4-aminophenylbispinacolate DBEDOT compound BDT10 .50.225 [mL] V [g] 0.75 m [mmol] n 1.00 0.125 eq. 0.75 1.00 Pd(PPh acid 4-nitrophenylboronic DBEDOT compound il:0% yield: il:0% yield: 3 3 ) ) 4 4 ◦ C hs eaaincudb bevdta aihdatraon 0minutes. 30 around after vanished that observed be could separation phase a .500 0.046 0.04 0.05 .500 0.087 0.08 0.05 iue9.32 Figure 3 7.50 ol eosre,idctn htteconditions the that indicating observed, be could 7.50 HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER 85 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. lwywre oro 0 room to warmed slowly dropwise a rprd(EE :)frwihtepoutwspeae n5go silica. of g 5 column on A prepared obtained. was was product oil drying The the brown and which a solid. phases solvent for brown the the 5:1) a removing separating (PE:EA and After before prepared suspension stirred brine sulphate. was yellow was magnesium with a solution over washed obtain the phase and to organic and THF water the obtained with mL was extracted 50 solution was on solution red after poured orange obtained dark was to a solution color The hours, changed to and 3 night. catalyst clear After over the turned solution and temperature. The 2,5-dibromothiophene room precipitate. adding to white before heating a minutes 0 and 45 to suspension for red cooled a stirred was obtain was suspension The solution The suspension. grey cannula. a a obtain to diethylether in suspended H.GCMS 8H). 0m he-ekfls ihtospusada ro ne a hre ihEO n 0m degassed mL 20 and EDOT -78 with to charged was cooled inlet argon was an solution and septums The two THF. with flask three-neck mL 50 A ytei f25D(,-tyeeixtinltipeeMto A Method 2,5-Di(3,4-ethylenedioxythienyl)thiophene of Synthesis Systems Trithiophene of Perparation 9.4.4 ,-irmtipee10 .00.28 2.50 NidppfCl THF 1.00 2,5-dibromothiophene DT30 .00.80 [mL] V 7.50 [g] m 3.00 [mmol] n eq. Et MgBr n EDOT compound BL .M33 .53.30 8.25 3.30 2.5M -BuLi 1 theory) of (% g 0,175 yield: 2 M 20Mz DMSO-d6): MHz, (250 NMR H O 2 via 2 yig.Tesihl elwslto a tre o 5mntsa h eprtr n then and temperature the at minutes 45 for stirred was solution yellow slightly The syringe. O 7)(87) (73) S O .20080.020 0.038 0.02 .082 1.519 8.25 3.30 ◦ 2) MgBr 45 min 1) BuLi,-78°C 45 min 0 °C C ycagn oa c ah nascn ak h ansu rmd was bromide magnesium the flask, second a In bath. ice an to changing by 2, Et 2 O δ ◦ .3(,2) .0–65 m H,43 dd 67 .,25Hz, 2.5 3.8, 26.7, = J (dtd, 4.32 2H), (m, 6.54 – 6.60 2H), (s, 7.13 C O sn naeoelqi irgnbt and bath nitrogen acetone/liquid an using S O MgBr iue9.33 Figure Br 20.00 10.00 (63) S THF NiCl Br 2 (dppe) HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER O S O (88) S O S O ◦ n C BL a added was -BuLi rnfrdusing transfered 86 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. tc oteflkwl.Terato a tre tR o or n a monitored was and hours 4 for RT NBS at where positions stirred at was argon separated reaction with precipitate The solution flushed black The was A wall. minutes. flask green. 10 flak washing dark over the gas portions to to small a yellow in stuck initial and added an inlet was from argon NBS color THF. an degassed changed septum, and ETE a with with charged flask and three-neck mL 50 A 0m he-ekfls iha ro ne,aspu n a ahn akwscagdwt EDOT with charged was flask washing gas a and -78 to septum cooled a was inlet, solution argon The THF. an degassed with dry and flask three-neck mL 50 A ett opout M ftebakpeiiaesoe,ta lgmrzto/oyerainoccured. oligomerization/polymeirzation yielded that but showed, freezer precipitate the black in some the stored mL of was 10 NMR solution to remaining volume product. washed The the THF, no reducing off. to with After filtered next extracted were sulphate. was and magnesium solution separated over The particles dried black being thiosulphate. before sodium brine saturated and of water with mL 50 in quenched being ytei f25D(,-tyeeixtinltipeeMto B Method 2,5-Di(3,4-ethylenedioxythienyl)thiophene of Synthesis amdt 0 to warmed dropwise added was irmtipeeadtectls.Tesseso a tre vrih.TCo h ecinindicated reaction 2,5-Di(3,4-ethylenedioxythienyl)thiophene the findings. of these of Bromination confirmed 2,5- TLC GCMS adding Reaction adding overnight. before obtained. stirred was hour was cannula progress 1 suspension reaction the for The no as stirred flow, that was catalyst. argon suspension under the obtained funnel and The a dibromothiophene process. using the transfered during was clogged suspension got The suspension. white a obtain ,-irmtipee10 .00.28 2.50 NidppfCl THF 1.00 2,5-dibromothiophene H 15.00 0.179 0.175 1.00 0.48 [mL] V 2.10 [g] 1.00 m THF [mmol] NBS n ETE eq. compound DT30 .00.80 [mL] V 7.50 [g] m 3.00 [mmol] n eq. MgBr n EDOT compound Et BL .M33 .53.30 8.25 3.30 2.5M -BuLi il:0% yield: 2 O 2 *Et 2 2 .082 1.519 8.25 3.30 O ◦ C na c ah nascn ak MgBr flask, second a In bath. ice an in via yig.Teslto a tre tta eprtr o 5mntsbfr being before minutes 45 for temperature that at stirred was solution The syringe. .20080.020 0.038 0.02 iue9.34 Figure 20.00 10.00 ◦ C 2 sn naeoelqi irgnbt and bath nitrogen acetone/liquid an using *Et 2 a ie ih1 Lo ityehrto diethylether of mL 10 with mixed was O HPE .EPRMNA PART EXPERIMENTAL 9. CHAPTER via CSbefore GCMS n -BuLi 87 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. ito Structures of List A Appendix B(OH) B(OH) (16) 1 (2) (1) O B O O (10) O B 2 2 H H O B 2 2 N N H H 2 2 N N 5 (6) (5) (17) HO HO NH NH 1)(12) (11) OH OH 2 2 CHO (13) N H (18) OH OH N N 2 N (HO) (HO) O 88 2 2 B B O N (19) 3 (4) (3) N H H N (21) N X CN 1)(15) (14) 7 (8) (7) O O B O OH OH B(OH) B(OH) (9) B O O 2 2 HO HO N (20) N HO HO O O N N OH OH Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. O O O HO H HO 3 N 3)(34) (33) (46) Si OH (23) 4)(3 4)(45) (44) (43) (42) Cl N H N OH (22) 3)(9 (40) (39) (38) O O O O (27) O NH NH (48a) N 3 O HOOC N H OOC Cl HO HO N Si OH N O Si OH (24) OH OH COO COOH (28) N (29) N N O O O O O N O 2 N SiO (35) R (48b) 2 OHC N HO N O O Cl (25) N OH CHO NO NO O O (47) N H 2 2 (30) 2 OH CHO N O O PEDXA ITO STRUCTURES OF LIST A. APPENDIX NHR NHR O O N 3)(37) (36) NO O O N 2 N NH HO (31) 2 H H 2 2 N N O O N N HOOC HOOC (26) OH OH OH N O N N OH (41) (49) N NH N NH NH 2 2 2 COOH COOH (32) O N O O N OH NHR NH NH 2 89 2 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. * MeO H R H 2 * N * 2 O N H N S (72) N N N S 6)(63) (61) 6)(69) (68) OMe N R H N NH O (50) 2 S N N NH 2 (78) n N H * S N R 2 5)(56) (55) R n * N OOH HO R * O N H N (73) N N S S NH NH N N H N R Br O N NH (62) 2 2 n * N N H 2 N H R (58) S NH R HOOC HOOC Br O O N H 2 * (74) n Br S N N * 7)(80) (79) BrZn N R S (51) S COOH COOH (70) N H Br O O R S R COOH COOH S N H Br NH NH Br Br N N O O 2 2 * N R 7)(76) (75) n N CN S N NH S S Br N H N Br 2 NH 6)(65) (64) S S S * 2 (52) R CN * Br A Br N H O PEDXA ITO STRUCTURES OF LIST A. APPENDIX O O S rBr Br N (59) S Hal H O Br 2 N O A n S N H N N O (81) (71) S (53) S N R Br N n O * Br O Br S O O N Hal (60) NH O (57) N R H N S 2 n S N O O R S 6)(67) (66) N Br S (77) O S H H N H 2 2 S N N R Br O O N N N (54) N N S N R O S N O S n * NH NH Br 90 2 2 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. Br N H HOOC 2 OOC O N O S S (82) 8)(88) (87) O O MgBr O O N NH S COO COOH 2 N Br O N O NH (91) H O 2 3 O N (93) N (83) HOOC S O OOC O O (92) O N Br S O O NH NH N 3 3 S O COOH COOH N O S NH O S (84) O O O 3 S N HOOC H OOC 2 Br N

O O N N 9)(5 (96) (95) (94) Br NO N S

N O O O

N N 2 PEDXA ITO STRUCTURES OF LIST A. APPENDIX NH (99)

(85)

N

NO S (89) COO COOH S 2

2 O H R

N 2 N H 2 S N N N O

O R NH N N N O Br 9)(98) (97) N CHO 2 S NH

O HOOC HOOC O NH 2 O O

(86) 2

N S H H

N N 2 N (90) (100) 2 N

N

NH R N N N N

2 N COOH N N

N COOH COOH NH NH

O 91 2 2 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. Polyimides B Appendix

Mass loss [%] 100 50 75 0 0 0 800 600 400 200 0 iueB.1: Figure TGA Temperature [°C] fTP:MA T TAPM:PMDA. of 92 D NSTR, ≈ 515 ◦ t C R . = 72h,200°C Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. iueB.3: Figure T-Ro AMPD at TAPM:PMDA of ATR-IR Transmission [%] Transmission [%] iueB.2: Figure 003500 4000 003500 4000 NSTR, NSTR, NSTR, Modelcompound,NSTR, ATR-IR t t t R R R = 2h,200°C = 6h,200°C = 72h,200°C fTP:MAat TAPM:PMDA of t R 2hadtemdlcmon bandatrHSo AMwt hhlcanhydride. phthalic with TAPM of HTS after obtained compound model the and h 72 = 0020 0010 1000 1500 2000 2500 3000 0020 0010 1000 1500 2000 2500 3000 Wavenumber [cm Wavenumber [cm t R t = 72h,200°C R n .Rdbxidctsrsda amines. residual indicates box Red h. 6 and h 2 =

O

O N -1 -1 ] ] PEDXB POLYIMIDES B. APPENDIX 500 500 93 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek.

Mass loss [%] 100 iueB.4: Figure 50 60 70 80 90 0 0 0 800 600 400 200 0 TGA fteTP:M ooe atA S rud170 around SSP A: salt monomer TAPM:PMA the of Temperature [°C] Monomer salt, t R = 24h,RT,upscale ◦ C PEDXB POLYIMIDES B. APPENDIX and T D ≈ 530 ◦ C 94 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek.

Mass loss [%] 100 iueB.5: Figure 50 60 70 80 90 0 0 0 800 600 400 200 0 TGA fteTP:M ooe atB S rud170 around SSP B: salt monomer TAPM:PMA the of Temperature [°C] Monomer salt, ◦ C t PEDXB POLYIMIDES B. APPENDIX and R = 24h,RT T D ≈ 530 ◦ C 95 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. iueB.6: Figure cue,ytteaiemdswr ucsflytasomdt moimmoieties. ammonium to transformed successfully were modes amine the yet occured, IR fteTP:M ooe at h bec faiemite swl siiemdsidctsta opolymerization no that indicates modes imide as well as moieties amine of absence The salt. monomer TAPM:PMA the of 0030 0020 0010 00500 1000 1500 2000 2500 3000 3500 4000

Transmission [%] 500 1000 1500 2000 2500 3000 3500 4000

t t t t R R R R = 24h,RT,stirred = 24h,RT,stirred = 24h,RT,stirred = 24h,RT,stirred Wavenumber [cm -1 ] PEDXB POLYIMIDES B. APPENDIX 96 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. disappeared. B.7: Figure PXRD fTiAMPD.Wt nraigcnetain h mrhu akrudicesdadcytliereflections crystalline and increased background amorphous the concentration, increasing With TrisAPM:PMDA. of

Intensity [a.u.] NSTR, NSTR, NSTR, NSTR, NSTR, 5 01 02 30 25 20 15 10 5 t t t t t R R R R R = 72h,200°C, = 72h,200°C, = 72h,200°C, = 72h,200°C, = 72h,200°C, 01 02 30 25 20 15 10 2 θ c c c c c Cu-K C = 5mmol/L50 = 10mmol/L = 20mmol/L = 30mmol/L = 40mmol/L α [°] PEDXB POLYIMIDES B. APPENDIX 97 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek.

Mass loss [%] 100 20 40 60 80 0 0 0 0 800 600 400 200 0 iueB.8: Figure TGA Temperature [°C] fteTrisAPM:PMDA. the of NSTR, T D ≈ 530 t R = 24h,200°C ◦ C PEDXB POLYIMIDES B. APPENDIX 98 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek.

Mass loss [%] 100 20 40 60 80 0 0 0 0 800 600 400 200 0 iueB.9: Figure TGA fTiAMPD oc screen. conc. - TrisAPM:PMDA of Temperature [°C] NSTR, c t R = 72h,200°C, T D ≈ 530 = 50mmol/L PEDXB POLYIMIDES B. APPENDIX ◦ C 99 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek.

iueB.10: Figure Intensity [a.u.] NSTR, NSTR, NSTR, 01 02 30 25 20 15 10 5 01 02 30 25 20 15 10 5 PXRD t t t R R R = 48h,200°C = 72h,200°C = 24h,200°C fTiAMMlAsoscmltl mrhu systems. amorphous completely shows TrisAPM:MellA of 2 θ Cu-K C α [°] PEDXB POLYIMIDES B. APPENDIX T D ≈ 530 ◦ C 100 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. iueB.11: Figure fCO of 2 : TGA Mass loss [%] fTrisAPM:MellA. of 100 20 40 60 80 0 0 0 0 800 600 400 200 0 T D ≈ 490 ◦ C h otnosms osbten100 between loss mass continuous The . Temperature [°C] NSTR, t R ◦ = 24h,200°C C ≤ PEDXB POLYIMIDES B. APPENDIX T ≤ 400 ◦ C ol niaeelimination indicate could 101 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. iueB.12: Figure UV/VIS

Intensity [a.u.] esrmnso Azsses sson VVSpoete a etndb uigtepr position. para the tuning by tuned be can properties UV/VIS shown, As systems. DATz of measurements 0 5 0 5 0 5 0 5 0 5 800 750 700 650 600 550 500 450 400 350 300 Wavenumber [nm] NO COOHPhTz BATB PEDXB POLYIMIDES B. APPENDIX 2 PhTz 102 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. iueB.13: Figure TGA

Mass loss [%] 100 50 75 fBT.Teiiilms-oscnb cone otefc htBATB*H that fact the to accounted be can mass-loss initial The BATB. of 0 0 600 400 300 0 0 200 100 Temperature [°C] 500 PEDXB POLYIMIDES B. APPENDIX BATB*H 2 a sdfrtemeasurement the for used was O 2 O 103 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. Crystallization C Appendix 104 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. 11H0276 .741)008(3 io0036 . . . . d 1 . 8 . 0.063(6) . d Uiso 1 . 0.0481(13) 8 0.0734(19) . 0.042(6) . 0.277(6) d Uiso H 1 . 0.1002(14) 8 . 0.1772(15) 0.027(4) d 0.781(5) Uiso 1 H 0.1799(10) 8 0.2422(14) 0.0106 0.847(5) Uiso H 0.426348 -0.157736 0.254726 H . . . . d 1 . 8 . 0.0117(3) . d Uani 1 . 0.15290(7) 4 0.18213(9) . 0.0101(4) 0.7473(3) . d Uani N 1 . 0.14903(8) 8 0 . 0.0092(3) 0.5 d Uani N 1 0.27982(6) 4 0.09753(8) 0.0179(4) 0.6054(3) Uani N 0 0.11833(11) 0.2050(4) O H1o1 H2n3 H1n3 H1c4 C4 C3 C2 C1 N3 N2 N1 O1 _atom_site_disorder_group _atom_site_disorder_assembly _atom_site_refinement_flags _atom_site_calc_flag _atom_site_occupancy _atom_site_site_symmetry_multiplicity _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_fract_z _atom_site_fract_y _atom_site_fract_x _atom_site_type_symbol _atom_site_label loop_ 8 7 6 5 4 3 2 orthorhombic 1 90 90 _space_group_symop_operation_xyz 15.915(5) 2n’ 90 2 _space_group_symop_id ’-P 11.628(4) m’ n loop_ n ’P 3.6751(11) _symmetry_space_group_name_Hall _symmetry_space_group_name_H-M symmetry_cell_setting _cell_angle_gamma _cell_angle_beta _cell_angle_alpha _cell_length_c _cell_length_b _cell_length_a BATB .573 00359 .53()Un .083 . . . . d 1 . 8 . 0.0088(3) . d Uani 1 . 0.45634(7) 4 -0.09345(9) . 0.0079(4) 0.3547(3) . d Uani C 1 . 0.41177(9) 8 0 . 0.0089(3) 0.5 d Uani C 1 0.19475(7) 4 0.09097(9) 0.0081(4) 0.6169(3) Uani C 0.31823(9) 0 0.5 C -x+1/2,y+1/2,z+1/2 x+1/2,-y+1/2,z+1/2 x,y,-z -x,-y,-z x+1/2,-y+1/2,-z+1/2 -x+1/2,y+1/2,-z+1/2 -x,-y,-z x,y,z PEDXC CRYSTALLIZATION C. APPENDIX 105 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. _atom_site_disorder_group _atom_site_disorder_assembly _atom_site_refinement_flags_occupancy _atom_site_refinement_flags_adp _atom_site_refinement_flags_posn _atom_site_calc_flag _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_fract_z _atom_site_fract_y _atom_site_fract_x _atom_site_type_symbol _atom_site_label loop_ 4 3 orthorhombic 31 2 90 90 1 2ac-2’ ’P _space_group_symop_operation_xyz 9.4253(11) 21’ 90 n m ’P loop_ 4.7453(5) _symmetry_space_group_name_Hall 18.630(2) _symmetry_space_group_name_H-M _space_group_IT_number symmetry_cell_setting _cell_angle_gamma _cell_angle_beta _cell_angle_alpha _cell_length_c _cell_length_b _cell_length_a 4NO2MPhTz -x,y,z x+1/2,-y,z+1/2 -x+1/2,-y,z+1/2 x,y,z PEDXC CRYSTALLIZATION C. APPENDIX 106 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. 1 .00019()070()004()Un . . P . T . S . . d U . 2 R . 1 calc Uani . 1 0.0149(3) . 1 . 0.7909(2) Uiso . d 0.1998(4) 0.021 . . 1 0.5000 0.7767 U 1 . C 0.2268 R Uani . 0.3909 calc 0.0173(3) H . 1 0.73969(16) . 1 0.2971(3) . . Uiso 0.43488(8) d P 0.018 C 1 C10 T 0.5970 1 S 0.5696 Uani d 0.3909 0.0149(2) 2 H 0.63307(15) H9 1 0.4995(3) . Uani 0.43506(7) . 0.0115(3) . C . . 0.57886(18) C9 . . U 0.6001(4) . R 0.5000 . U calc C R . H8 1 calc . 1 1 d Uiso 1 1 0.020 C8 Uiso 1 0.3919 . 0.020 Uani 0.9794 0.3999 . 0.0168(3) 0.3109 . . 1.3152 . 0.33464(16) C7 H . 0.3021 . U 1.1541(3) . H R 0.30911(7) . U calc C R . H6AB 1 calc . 1 1 d Uiso 1 1 0.021 H6A Uiso 1 0.2841 . 0.021 Uani 1.1330 0.1747 . 0.0175(3) 0.2011 . . 0.9629 . 0.23065(18) H C6 . 0.2506 . U 1.1389(3) . H R 0.24684(7) . U calc C R . H5AB 1 calc . 1 1 d Uiso 1 1 0.025 H5A Uiso 1 0.0031 . 0.025 Uani 1.2079 -0.0095 . 0.0206(3) 0.3170 . . 1.5432 . 0.05832(18) C5 H . 0.3099 . U 1.3841(3) . H R 0.31165(8) . U calc C R . H4AB 1 calc . . 1 1 . d Uiso 1 P . 1 0.019 H4A Uiso T 1 0.2049 . 0.019 S Uani 1.6020 . 0.0982 d 0.0157(3) 0.3730 1.4161 2 . 0.15475(16) H C4 0.4206 1 1.4190(3) . . H Uani 0.37583(7) d . 0.0106(3) C 1 P . 0.46353(19) H3AB 1 T 0.8141(4) . Uani S 0.5000 . 0.0110(2) d C . 0.31152(13) H3A 2 . 1.0937(3) 1 . . 0.43954(7) Uani . d C 0.0205(4) C3 1 . 0.90091(19) 1 . -0.0204(4) . Uani . 0.5000 d 0.0135(2) P . N C2 1 0.25737(13) T 1 . 1.1885(2) S Uani 0.37631(6) . d 0.0122(2) N C1 2 . 0.41730(12) 1 0.9002(3) . Uani 0.43583(6) d 0.0118(3) N 1 N4 0.25452(18) 1 1.1956(3) Uani 0.5000 0.0286(3) N N3 0.94392(15) -0.1066(3) 0.44166(8) 0.0213(2) O N2 0.13649(14) 1.3745(2) 0.24608(6) O N1 O2 O1 ai11d...... d 1 1 Uani PEDXC CRYSTALLIZATION C. APPENDIX 107 Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. Bibliography 1]G h,H Ren, H. Zhu, G. [13] 1]F ho .Lu .Mte .Dn,J Zhang, J. Dong, A. Mathe, S. Liu, H. Zhao, F. [11] 1]C .Decs .M Yaghi, M. O. Diercks, S. C. [12] 1]Y-.Zag .S,H uuaa .Yn .Gnaa .Dog .Zu .M Yaghi, M. O. Zou, X. Duong, A. Gándara, F. Yun, Y. Furukawa, H. Su, J. Zhang, Y.-B. [15] 1]Y h,S a,Y i,W Zhang, W. Jin, Y. Wan, S. Zhu, Y. [14] 1]A .Cote, P. A. [10] 1]F .UieRm,J .Hn,H uuaa .Kök .OKee .M Yaghi, M. O. O’Keeffe, M. Klöck, C. Furukawa, H. Hunt, R. J. Uribe-Romo, J. F. [16] 1]Q ag .Wn,S u .B apr .Zun,J hn,H u,S i,Y Yan, Y. Qiu, S. Guo, H. Zheng, J. Zhuang, Z. Kaspar, B. R. Gu, S. Wang, J. Fang, Q. [17] 2]L h,Y-.Zhang, Y.-B. Zhu, L. [27] 2]S admeh .Mlik .Lks,M .Mn,T en,R Banerjee, R. Heine, T. Mane, V. M. Lukose, B. Mallick, A. Kandambeth, S. [29] 2]S admeh .B hne .K ad,B uoe .Hie .Banerjee, R. Heine, T. Lukose, B. Panda, K. M. Shinde, B. D. Kandambeth, S. [28] Zhang, W. Denman, J. R. Yu, C. Jin, Y. [18] 2]P un .Atnet,A Thomas, A. Antonietti, M. Kuhn, P. [22] 2]L .Lni .W ifr,M hrty .J Lavigne, J. J. Bharathy, M. Tilford, W. R. Lanni, M. L. [26] 1]S admeh .Mlik .Lks,M .Mn,T en,R Banerjee, R. Heine, T. Mane, V. M. Lukose, B. Mallick, A. Kandambeth, S. [19] 2]J .Hn,C .Doa,J .LVni,A .Ct,O .Yaghi, M. O. Côté, P. A. LeVangie, D. J. Doonan, J. C. Hunt, R. J. [25] 3]L rl,M yr .Lffrnz .Prsn .V ees .Hecht, S. Peters, V. M. Persson, M. Lafferentz, L. Dyer, M. Grill, L. [30] 3]X eg .Dn,D Jiang, D. Ding, X. Feng, X. [31] 2]J u,Y u .Jn .Ce,T ai .Hnh,M .Adca,J i,A ak,H he .Sk,S re .Hrmt,J Gao, J. Hiramoto, M. Irle, S. Seki, S. Ihee, H. Saeki, A. Kim, J. Addicoat, A. M. Honsho, Y. Kaji, T. Chen, L. Jin, S. Xu, Y. Guo, J. [21] 2]Q ag .Zun,S u .B apr .Zeg .Wn,S i,Y Yan, Y. Qiu, S. Wang, J. Zheng, J. Kaspar, B. R. Gu, S. Zhuang, Z. Fang, Q. [20] 2]R uze,H ac,G dr .Kot .M ek,M Lackinger, M. Heckl, M. W. Kloft, S. Eder, G. Walch, H. Gutzler, R. [23] 3]S e,M .Bjy,R asn .Lyor,Y .Kiyk .J dm,A .Cooper, I. A. Adams, J. D. Khimyak, Z. Y. Laybourn, A. Dawson, R. Bojdys, J. M. Ren, S. [32] 2]D cwr,Y oa .Kod,K cwroáPcoá .Trbk .Rbčk .Jnue,F io,M .Oaaek,J. Opanasenko, V. M. Simon, F. Janoušek, J. Rybáček, J. Tarábek, J. Schwarzová-Pecková, K. Klouda, J. Noda, Y. Schwarz, D. [24] 1 .K A. [1] 2 .Wöhler, F. [2] 9 .M ah,M .Kluzi .S Diercks, S. C. Kalmutzki, J. M. Yaghi, M. O. [9] 4 .R ce,M Zanger, M. McKee, R. J. [4] 8 .P iwl .Cada .Knabt,B uoe .Hie .Banerjee, R. Heine, T. Lukose, B. Kandambeth, S. Chandra, S. Biswal, P. B. [8] 6 .M Hergenrother, M. P. [6] 3 .Baeyer, A. [3] 7 .Bugrnr .J ods .M Unterlass, M. M. Bojdys, J. M. Baumgartner, B. [7] 5 .Staudinger, H. [5] .Jiang, D. ek,A caja .Shit .Sle .Rie-cee,N eei,J .Rb,P crhr,J e .Plzj .Nachtigall, P. Polozij, M. He, J. Ecorchard, P. Rabe, P. J. Severin, N. Reiter-Scherer, V. Bojdys, Selve, J. S. M. Schmidt, J. Acharjya, A. Čejka, ekulé, a.Commun. Nat. n.drCei n Pharm. und Chemie der Ann. n.drPy.udChemie und Phys. der Ann. eihedrDsh hm Gesellschaft Chem. Dtsch. der Berichte cec 8- ). (80-. Science d.Mater. Adv. eihedrDsh hm eelcat( Ser. B (A Gesellschaft Chem. Dtsch. der Berichte oosOgncFrameworks Organic Porous ihProm Polym. Perform. High Molecules 2013 .Ce.Educ. Chem. J. 2017 2005 hm o.Rev. Soc. Chem. cec 8- ). (80-. Science , 4 , 2017 2736. , 29 , .A.Ce.Soc. Chem. Am. J. 310 1703399. , ne.Cei n.Ed. Int. Chemie Angew. , 1166–1170. , hm o.Rev. Soc. Chem. 22 1828 1991 1857 1149. , 2003 2017 2012 nrdcint eiua Chemistry Reticular to Introduction , pigrBri edleg eln Heidelberg, Berlin, Heidelberg, Berlin Springer , , 88 Nanomaterials , 68 104 , oy.Chem. Polym. 253–256. , , A242. , , 15 355 41 129–150. , 1871 2015 3–45. , 6010. , .A.Ce.Soc. Chem. Am. J. eaal1585. , 2013 , , 108 4 137 2008 555–558. , , 42 2017 13772–13775. , 2014 6634. , .A.Ce.Soc. Chem. Am. J. , 1920 47 , a.Nanotechnol. Nat. , hm Commun. Chem. 8 3450–3453. , 5 15. , 3771–3776. , , 2011 53 1073–1085. , .A.Ce.Soc. Chem. Am. J. .A.Ce.Soc. Chem. Am. J. a.Commun. Nat. .A.Ce.Soc. Chem. Am. J. , ne.Cei n.Ed. Int. Chemie Angew. 133 .A.Ce.Soc. Chem. Am. J. , 2019 13975–13983. , 2008 .A.Ce.Soc. Chem. Am. J. .A.Ce.Soc. Chem. Am. J. 2009 . 2007 d.Mater. Adv. , 130 4456. , 2014 , 2012 2012 11872–11873. , 2 2015 687–691. , 2013 , 5 2009 4503. , , , 134 134 . 2012 , 2013 135 2013 2015 , 19524–19527. , 19524–19527. , 131 5328–5331. , , , 24 , , 135 4570–4571. , 52 137 2357–2361. , 13052–13056. , 16336–16339. , 8352–8355. , Die approbierte gedruckte Originalversion dieser Diplomarbeit ist an der TU Wien Bibliothek verfügbar. The approved original version of this thesis is available in print at TU Wien Bibliothek. 3]M uia .J wn .Wsiu .Ogura, K. Washizu, S. Kwon, J. Y. Fujita, M. [36] 3]C .Cny .A Cox, A. P. Cundy, S. C. [35] 3]D .Hwhre .H ogi,M .Jcsn .W oe,T .Morton, C. T. Loder, W. J. Jackson, B. M. Hodgkin, H. J. Hawthorne, G. D. [37] 3]R .Luie .A Ballman, A. A. Laudise, A. R. [34] 4]M eas,E .Frank, U. E. Uematsu, M. [41] 3]J heai .Do .M rt,J .Hodgkin, H. J. Groth, M. A. Dao, B. Chiefari, J. [38] 3]L emoe,B amate,M uhegr .Pohsa .Knge,M .Unterlass, M. M. Konegger, T. Prochaska, T. Puchberger, M. Baumgartner, B. Leimhofer, L. [39] 4]M .Unterlass, M. M. [40] 4]W .Mrhl,E .Franck, U. E. Marshall, L. W. [42] 3]J F. J. [33] 4]B amate,A vroa .Bnigr .Hmte,M acet-ecmn,M .Unterlass, M. M. Marchetti-Deschmann, M. Hametner, C. Bintinger, J. Svirkova, A. Baumgartner, B. [43] 5]G Inzelt, G. [57] 4]D aiet,T ai,E ees .Hly .Asnal,J .Wuest, D. J. Arseneault, M. Helzy, F. Demers, E. Maris, T. Laliberté, D. [44] 5]J .Joule, A. J. [58] 6]L reeda,F oa,D ria,H ilrzk .R Reynolds, R. J. Pielartzik, H. Freitag, D. Jonas, F. Groenendaal, L. [63] 5]X u .Za,X eg .Ya,S i,L og .Hu, Y. Song, L. Qiu, S. Yuan, B. Feng, X. Zhan, J. Mu, X. [56] 6]R .Lee .M hrosy .D McCullough, D. R. Khersonsky, M. S. Loewe, S. R. [62] 5]M .Tuledr .Gökhfr .MrhtiDshan .M Unterlass, M. M. Marchetti-Deschmann, M. Glöcklhofer, F. Taublaender, J. M. [55] 6]S a,D .Catre,R hs,A .Nandi, K. A. Ghosh, R. Chatterjee, P. D. Das, S. [60] 6]M .Dn,L ish .Wantz, G. Hirsch, L. Dang, T. M. [61] 5]K aeo .Ysio .Inuishi, Y. Yoshino, K. Kaneto, K. [59] 4]L .Kh .Eriks, K. Koh, L. L. [45] 4]L u .Lu .Wn,S a,X h,J Yang, J. Shi, X. Yan, S. Wang, F. Liu, R. Xu, L. [49] 6]M oeat,Y hn,R .Ksm .L Elsenbaumer, L. R. Kasim, K. R. Cheng, Y. Pomerantz, M. [64] 5]J i .Fn,L i .Wn,S in,Y e .Lu .Wu, L. Liu, M. He, Y. Liang, S. Wang, J. Li, L. Fang, W. Bi, J. [50] 5]M uzOé,N ozlzLkna .Slns .Gudn .Anu .E Ortega, E. J. Arnau, A. Gourdon, A. Silanes, I. González-Lakunza, N. Ruiz-Osés, M. [54] 5]P uhaa,Y-.Le .Zag .S Ahn, W.-S. Zhang, S. Lee, Y.-R. Puthiaraj, P. [51] 4]B amate,M uhegr .M Unterlass, M. M. Puchberger, M. Baumgartner, B. [46] 5]S u,L tgae,H h .Hrce,B .Lotsch, V. B. Hirscher, M. Oh, H. Stegbauer, L. Hug, S. [53] 4]Y hn,S Jin, S. Zhang, Y. [48] 6]M .Pptn,K apaeta,S .Hrae,R .Gregory, V. R. Hardaker, S. S. Eaiprasertsak, K. Pepitone, F. M. [67] Wudl, F. Perepichka, F. D. Meng, H. [65] 5]M i,L u,S i,B Tan, B. Jin, S. Guo, L. Liu, M. [52] 4]M Gomberg, M. [47] 6]Y i,Z i .Jn .Ts,J Xia, J. Tusy, C. Jin, J. Li, Z. Yin, Y. [66] Nano 16335. 1229–1232. intae,A .Gge,A .Gez .Kohl .Bi,A ypn .Rihmir .M ek,M Lackinger, M. Heckl, M. W. Reichlmaier, S. Lyapin, A. Bein, T. Knochel, P. Goetz, J. A. Gigler, M. A. Dienstmaier, 2011 .Eetohm c.Eng. Sci. Electrochem. J. Thiophenes , 5 .A.Ce.Soc. Chem. Am. J. 9737–9745. , oyes(Basel). Polymers ne.Cei n.Ed. Int. Chemie Angew. caCytlor et tut rsalg.Cyt Chem. Cryst. Crystallogr. Struct. B Sect. Crystallogr. Acta E. .A ol) pigrItrainlPbihn,Cham, Publishing, International Springer Joule), A. J. (Ed.: , hm Rev. Chem. .Py.Ce.Rf Data Ref. Chem. Phys. J. .A.Ce.Soc. Chem. Am. J. .Py.Ce.Rf Data Ref. Chem. Phys. J. .Mtr hm A Chem. Mater. J. 1898 d.Mater. Adv. oi tt Commun. State Solid yt.Met. Synth. 2017 2018 2003 ne.Cei n.Ed. Int. Chemie Angew. , 20 DOI , , , 773–780. , 2018 11 103 31. , .A.Ce.Soc. Chem. Am. J. .Mtr hm A Chem. Mater. J. 2011 663–702. , S Adv. RSC 10.5599/jese.448 2013 , ihProm Polym. Perform. High 1958 57 2019 S Adv. RSC 2292–2294. , oy.Chem. Polym. , d.Mater. Adv. 1980 23 , , 175 , 80 3597–3602. , 7 1981 1983 hm Mater. Chem. 5153–5172. , 2019 2655–2657. , , 97–102. , C pl ae.Interfaces Mater. Appl. ACS .Mtr Chem. Mater. J. 9 2015 1291–1306. , , , 2003 arml ai Commun. Rapid Macromol. 10 46 , 1994 9 1999 2016 , 295–304. , 389–391. , 1586–1590. , 2015 r.Lett. Org. 5 , . d.Mater. Adv. 20160–20177. , 42 , , , 116 2003 2015 11 658–661. , 4 , 16288–16311. , 6 rs.Got Des. Growth Cryst. 250–253. , 5773–5781. , 1151–1152. , ihProm Polym. Perform. High 1999 , 2003 , 15 27 ne.Cei n.Ed. Int. Chemie Angew. 1971 269–279. , 2000 8001–8010. , , , 9 2155–2163. , 5 2015 3229–3232. , .Py.Ce.B Chem. Phys. J. , , 27 12 2017 1405–1413. , 481–494. , . 2015 , .Mtr hm A Chem. Mater. J. 2005 9 , 23017–23026. , 36 1994 , 1799–1805. , 5 1451–1456. , hm Commun. Chem. 2006 , 2018 6 287–301. , BIBLIOGRAPHY , , 110 57 2017 12270–12274. , 25573–25577. , , 5 2017 16326– , 109 ACS , 53 ,