DOCSLIB.ORG

Alkali Metal Complexes of an Enantiopure Iminophosphonamide Ligand with Bright Delayed Fluorescence

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Alkali Metal Complexes of an Enantiopure Iminophosphonamide Ligand with Bright Delayed Fluorescence Chemical Volume 10 Number 18 14 May 2019 Pages 4717–4932 Science rsc.li/chemical-science ISSN 2041-6539 EDGE ARTICLE Peter W. Roesky et al. Alkali metal complexes of an enantiopure iminophosphonamide ligand with bright delayed fl uorescence Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue Alkali metal complexes of an enantiopure iminophosphonamide ligand with bright delayed Cite this: Chem. Sci.,2019,10,4742 fl † All publication charges for this article uorescence have been paid for by the Royal Society a a a a of Chemistry Thomas J. Feuerstein, ‡ Bhupendra Goswami,‡ Pascal Rauthe, Ralf Koppe,¨ Sergei Lebedkin,b Manfred M. Kappesbc and Peter W. Roesky *a The enantiomerically pure ligand P,P-diphenyl-N,N0-bis((R)-1-phenylethyl)phosphinimidic amide (1; (R)- HPEPIA) was synthesized and subsequently deprotonated with alkali metal precursors to yield dimeric complexes [M2{(R)-PEPIA}2](M¼ Li (2), Na (3), K (4), Rb (5)). The cesium compound [M{(R)-PEPIA}] (6) crystallized as a cocrystal composed of dimeric ([Cs2{(R)-PEPIA}2](6d) and 1D-polymeric ([Cs{(R)- PEPIA}]n)(6p) species in a 1 : 1 ratio. The coordination polymer 6p features a unique sinus-shaped configuration of repeating –Cs–N–P–N–Cs–N–P–N– units. Unusual photoluminescence (PL) properties were found for solid 1–6: in contrast to the fluorescent ligand 1, the alkali metal complexes Creative Commons Attribution 3.0 Unported Licence. show phosphorescence at low temperatures (<100 K) and thermally activated delayed fluorescence (TADF) above 150 K. The latter provides for PL quantum yields up to 36% (3) at ambient temperature. Received 4th February 2019 DFT calculations support that both 1 and 2–6 have similar singlet and triplet excited states with energy Accepted 11th March 2019 d separations of a few tens of meV. The strongly enhanced intersystem crossing (ISC) in the metal DOI: 10.1039/c9sc00629j complexes, resulting in TADF, is attributed to their dimeric structure. This suggests that the fluorophore rsc.li/chemical-science dimerization may serve as a tool to effect ISC for the design of TADF emitters. Introduction alkali metals and other elements,11,12 which are dealing with This article is licensed under a achiral versions of iminophosphonamides. However, the In coordination chemistry, mono anionic chelating nitrogen chemistry with chiral iminophosphonamide ligands is still donor ligands such as b-ketiminates,1 aminotroponimates2 nearly dormant. In 2007, racemic trans-1,2-diaminocyclohexyl- 3 4 linked N-aryl bis(iminophosphonamines) and subsequent Open Access Article. Published on 09 Elba 2019. Downloaded 25/09/2021 7:43:23 PM. bis(phosphinimino)methanides, amidinates and closely related guanidinates4f,4h,5 have been widely used to stabilize complexes with group 3 and group 13 elements were reported by 13 metal complexes.6 Among these ligands, NXN type donor Hill et al. More recently, Li and Guan reported on yttrium and ligands are particularly versatile because of their ability to alkaline earth metal complexes of chiral iminophosphonamides stabilize metal complexes by pincer-type coordination to form and their application as catalysts in cross-dehydrogenative 14 four-membered metallacycles. Furthermore, ne tuning of the coupling reactions of amines. In both reports, the chiral donor properties of NXN ligands by varying X {e.g., X ¼ BR center was solely introduced at one nitrogen atom of the NPN (boraamidinate),7 CR (amidinate),4a–e N (triazenide),8 SR (sul- ligand. To the best of our knowledge, chiral iminophosphona- 9 10 11 namidinate) and PR2 (iminophosphonamide)} is possible. mides bearing chiral centers at both nitrogen atoms have not The iminophosphonamides (NPN) having the general formula been known up to now. Moreover, there have been no reports on 0 À [R2P(NR )2] can be considered as the nitrogen analogues of chiral alkali metal iminophosphonamides. phosphinate anions, in which oxygen atoms are replaced by two Recently, we described the chiral version of an amidinate 15 amide groups. There are many reports on the complexes of ligand bearing chiral centers on both nitrogen atoms, and its rare earth metal complexes which served as suitable catalysts 16 aInstitute for Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstr. for the asymmetric intramolecular hydroamination, as well as 17 15, 76131 Karlsruhe, Germany. E-mail: [email protected] for the ring opening polymerisation of rac-lactide. These bInstitute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Hermann-von- results directed our attention to the synthesis of a chiral version Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany of an iminophosphonamide ligand, since this would show cInstitute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber- distinct structural (and complexation) features in comparison Weg. 2, 76131 Karlsruhe, Germany with amidinate ligands. Indeed, the commonly observed X–N † Electronic supplementary information (ESI) available. CCDC 1892950–1892955. bond length for amidinates (X ¼ CR) is 1.33 A˚ as compared to For ESI and crystallographic data in CIF or other electronic format see DOI: ˚ ¼ 10.1039/c9sc00629j 1.60 A in the case of iminophosphonamides (X PR2). As – – ‡ These authors contributed equally. a result, the latter ligands show wider N M N bite angles, 4742 | Chem. Sci.,2019,10,4742–4749 This journal is © The Royal Society of Chemistry 2019 View Article Online Edge Article Chemical Science where M is the coordinated metal atom. Furthermore, they In consistence, six signals were detected in the 13C{1H} NMR d ¼ exhibit a higher steric demand in the backbone, due to the spectrum in pairs for the CH3 ( (C6D6) 30.8, 25.9 ppm), CH d ¼ central quaternary P atom. ( (C6D6) 54.1, 49.9 ppm) and benzyl ipso-Cq carbon atoms 0 d ¼ Herein, we report on the synthesis of P,P-diphenyl-N,N - ( (C6D6) 152.7, 146.6 ppm). Furthermore, the NH proton was bis((R)-1-phenylethyl)phosphinimidic amide (1; (R)-HPEPIA) – observed as a broad singlet at 2.70 ppm in the 1H NMR spec- the rst enantiopure iminophosphonamide with chiral trum. In the FT-IR spectrum of 1 the corresponding NH À substituents at both nitrogen atoms. Subsequent deprotonation stretching mode was found at 3362 cm 1. Colorless single with common precursors of alkali metals led to the dimeric crystals of 1, suitable for X-ray structure analysis, were grown alkali metal derivatives. Investigation of their photo- from n-heptane. Compound 1 crystallizes solvent-free in the luminescence (PL) properties in the solid state supported by monoclinic chiral space group P21 with four molecular entities DFT calculations revealed a quite interesting behavior. The in the asymmetric unit cell (Fig. 1). The P1–N1 bond length of alkali metal compounds show bright PL which is contributed by 1.682(3) A˚ is in the range for a P–N single bond, while the P1–N2 phosphorescence at low temperatures and thermally activated bond length of 1.561(3) A˚ is in the range of a P–N double bond, delayed uorescence (TADF) above 150 K. Small (metallo) therefore the hydrogen atom was clearly assigned to the organic molecules, which exhibit TADF have recently attracted nitrogen atom N1. The N1–P1–N2 angle of 121.6(2) is compa- special attention because of their application potential for rable to that in similar compounds.10 organic light-emitting diodes.18 Their advantage lies in the fact Subsequently, we deprotonated the enantiopure ligand (R)- 1 that the TADF mechanism allows in principle for PL quantum HPEPIA ( ) and obtained the dimeric compounds [M2{(R)- ¼ 2 3 4 5 yields approaching 100%, due to fast intersystem crossing (ISC) PEPIA}2](M Li ( ), Na ( ), K ( ), Rb ( )) and [Cs2{(R)- 6 between singlet (S1) and triplet (T1) excited states with close PEPIA}2]/[Cs{(R)-PEPIA}]n ( ) using the common alkali metal 19 energy levels. To the best of our knowledge, this is the rst precursors n-BuLi, NaH, KH, and MN(SiMe3)2 (M ¼ Rb, Cs) example of TADF emitters based on the iminophosphonamide (Scheme 2). The synthesis of 5 and 6 could also be performed 1 Creative Commons Attribution 3.0 Unported Licence. derivatives. The fast ISC in these compounds is attributed to directly with elemental Rb and Cs (Scheme 2). In contrast to , their dimeric structure facilitating intramolecular charge sharp signals with well resolved ne couplings were observed transfer upon photoexcitation.20 The pronounced effect of the for the alkali salts 2–6 in the 1H NMR spectra. The CH proton 3 uorophore dimerization on the ISC parameters may be useful was detected as a doublet of quartets due to JPH coupling for the design of other efficient TADF materials. (conrmed by 1H{31P} NMR) across the nitrogen and phos- 3 phorousatoms,aswellasdueto JHH coupling with the CH3 protons. The absence of the NH proton in the 1H NMR spectra Results and discussion along with the lack of a NH stretching mode in the FT-IR Synthesis and characterization spectra indicate full deprotonation of the ligand in all This article is licensed under a compounds. For compounds 3–6 only one singlet was 0 The enantiopure ligand P,P-diphenyl-N,N -bis((R)-1-phenylethyl) observed in the 31P{1H} NMR spectra. 1 phosphinimidic amide ( , (R)-HPEPIA) was synthesized in In contrast, the 31P{1H} NMR spectrum of compound 2 a Staudinger reaction from the known compounds (R)-a-meth- 2 Open Access Article. Published on 09 Elba 2019. Downloaded 25/09/2021 7:43:23 PM. showed a pseudo-quartet, which was assigned to JPLi coupling 21 22 ylbenzyl azide and HN(R-CHMePh)(PPh2) (Scheme 1). The NMR spectrum of 1 is complex and strongly solvent dependent, which apparently results from (E)/(Z) isomerization and tautomerization (Scheme 1). In the 1H NMR spectrum broad signals without ne coupling were observed, similar to the results for the methylbenzyl substituted amidine (R,R)-N,N- 15 bis-(1-phenylethyl)benzamidine.
Load more

Recommended publications
  • Synthesis, X-Ray Structure and Properties of a Calcium(II) Coordination Polymer Showing Μ2-Η :Η and Μ3-Η :Η Coordination M
    Ms. Ref. No.: POLY-D-08-00248 (REVISED PAPER) Published in Polyhedron: 27(15); 2008; 3299-3305 Synthesis, X-ray structure and properties of a 1 1 calcium(II) coordination polymer showing µ2-η :η 2 1 and µ3-η :η coordination modes of 4-nitrobenzoate ∗ BIKSHANDARKOIL R SRINIVASAN , SANTOSH Y SHETGAONKAR, JYOTI V SAWANT, PALLEPOGU RAGHAVAIAH a Department of Chemistry, Goa University, Goa 403206 India email: [email protected] aPresent address: School of Chemistry, University of Hyderabad, Hyderabad, India 500 046 Abstract 1 2 The reaction of the monomeric compound [Ca(H 2O) 4(η -4-nba)( η -4-nba)] 1 (4-nba = 4-nitrobenzoate) with N-methylimidazole (N-MeIm) or imidazole (Im) at 100 oC results in the formation of the anhydrous mixed ligand complexes of composition [Ca(L)(4- nba) 2] (L=N-MeIm 2; L=Im 3). The compounds were characterized by elemental analysis, IR, UV-Vis and 1H NMR spectra, TG-DSC thermograms, weight loss studies and the structure of 2 was determined by single crystal X-ray crystallography. Compounds 2 and 3 can be transformed into 1 by heating with water. At elevated temperatures all compounds ( 1-3) are thermally decomposed to CaO. Compound 2 crystallizes in the centrosymmetric triclinic space group P ī with all atoms located in general positions. The structure reveals that 2 is a polymer and can be formulated as 1 1 2 1 catena -poly[[(N-methylimidazole)calcium(II)]( µ2-η :η -4-nitrobenzoato)( µ2-η :η -4- 1 1 2 1 nitrobenzoato)] . The structure of [[Ca(N-MeIm)]( µ2-η :η -4-nba)( µ3-η :η -4-nba)] n 2 2 consists of a central Ca(II) ion, a terminal N-MeIm ligand and two crystallographically independent 4-nba ligands.
    [Show full text]
  • Sonochemical Synthesis of Cadmium(II) Coordination Polymer Nanospheres As Precursor for Cadmium Oxide Nanoparticles
    crystals Article Sonochemical Synthesis of Cadmium(II) Coordination Polymer Nanospheres as Precursor for Cadmium Oxide Nanoparticles Farhad Akbari Afkhami 1 , Ali Akbar Khandar 1, Ghodrat Mahmoudi 2,* , Reza Abdollahi 3, Atash V. Gurbanov 4,5 and Alexander M. Kirillov 5,6,* 1 Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, 51666-16471 Tabriz, Iran; [email protected] (F.A.A.); [email protected] (A.A.K.) 2 Department of Chemistry, Faculty of Science, University of Maragheh, 55181-83111 Maragheh, Iran 3 Department of Physical Chemistry, Faculty of Chemistry, University of Tabriz, 51666-16471 Tabriz, Iran; [email protected] 4 Department of Organic Chemistry, Baku State University, Z. Khalilov str. 23, AZ 1148 Baku, Azerbaijan; [email protected] 5 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal 6 Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya st., Moscow 117198, Russia * Correspondence: [email protected] (G.M.); [email protected] (A.M.K.) Received: 15 March 2019; Accepted: 2 April 2019; Published: 9 April 2019 Abstract: Nanospheres of a new coordination polymer {[Cd2(µ-HL)(µ-L)(NO3)3(H2O)]·H2O}n (1) were easily prepared by a sonochemical method from cadmium(II) nitrate and HL (HL, pyridine-2-carboxaldehyde isonicotinoyl hydrazone) in ethanol. Single crystals of 1 were also obtained using a branched tube method. The crystal structure of 1 indicates that the µ-HL/µ-L− blocks act as linkers between the Cd(II) centers, assembling them into 1D tooth-shaped interdigitated chains, which are further interlinked into a complex 3D H-bonded network with a rare hms (3,5-conn) topology.
    [Show full text]
  • Porous Coordination Polymers with Ubiquitous and Biocompatible Metals and a Neutral Bridging Ligand
    ARTICLE Received 30 Apr 2014 | Accepted 14 Nov 2014 | Published 16 Jan 2015 DOI: 10.1038/ncomms6851 OPEN Porous coordination polymers with ubiquitous and biocompatible metals and a neutral bridging ligand Shin-ichiro Noro1,2,3,4, Junya Mizutani2, Yuh Hijikata5, Ryotaro Matsuda3,6, Hiroshi Sato6, Susumu Kitagawa6, Kunihisa Sugimoto7, Yasutaka Inubushi8,w, Kazuya Kubo1,2 & Takayoshi Nakamura1,2 The design of inexpensive and less toxic porous coordination polymers (PCPs) that show selective adsorption or high adsorption capacity is a critical issue in research on applicable porous materials. Although use of Group II magnesium(II) and calcium(II) ions as building blocks could provide cheaper materials and lead to enhanced biocompatibility, examples of magnesium(II) and calcium(II) PCPs are extremely limited compared with commonly used transition metal ones, because neutral bridging ligands have not been available for magnesium(II) and calcium(II) ions. Here we report a rationally designed neutral and charge-polarized bridging ligand as a new partner for magnesium(II) and calcium(II) ions. The three-dimensional magnesium(II) and calcium(II) PCPs synthesized using such a neutral ligand are stable and show selective adsorption and separation of carbon dioxide over methane at ambient temperature. This synthetic approach allows the structural diversification of Group II magnesium(II) and calcium(II) PCPs. 1 Research Institute for Electronic Science, Hokkaido University, Sapporo 001-0020, Japan. 2 Graduate School of Environmental Earth Science, Hokkaido University, Sapporo 060-0810, Japan. 3 PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi 332-0012, Japan. 4 Creative Research Institute (CRIS), Hokkaido University, Sapporo 001-0021, Japan.
    [Show full text]
  • A Cd(II) Coordination Polymer Based on Mixed Ligands: Synthesis, Crystal Structure, and Properties
    crystals Article A Cd(II) Coordination Polymer Based on Mixed Ligands: Synthesis, Crystal Structure, and Properties Shuai-Shuai Han, Zi-Wei He, Lei Li and Shui-Sheng Chen * College of Chemistry and Chemical Engineering, Fuyang Normal University, Fuyang 236041, China; [email protected] (S.-S.H.); [email protected] (Z.-W.H.); [email protected] (L.L.) * Correspondence: [email protected] Received: 11 November 2019; Accepted: 25 November 2019; Published: 27 November 2019 Abstract: A new coordination polymer, namely, [Cd(L)(frda)(H O)] 0.5L H O(1) was synthesized 2 · · 2 by hydrothermal reaction based on mixed multi-N donor 1-(4-(1H-imidazol-5-yl) phenyl)-1H- 1,2,4-triazole (L) and O-donor 2,5-furandicarboxylic acid ligands (H frda) with CdCl 2.5H O. 2 2· 2 Compound 1 was characterized by single-crystal x-ray diffraction, elemental analysis, and IR 2 spectroscopy. In 1, both the multi-N donor and O-donor frda − ligands act as linear two-connectors to bridge Cd(II) atoms, forming a two-dimensional (2D) layer. Interestingly, the parallel 2D layers stack in an AAA mode, and the infinite one-dimensional (1D) channels formed along the a-axis ··· direction, where the uncoordinated L molecules were embedded in the void. Furthermore, the weak interactions including the rich hydrogen bonding and π π stacking interactions progress the 2D − structure into a three-dimensional (3D) supramolecular polymer. Diffuse reflectance spectra and the luminescent property were also investigated. Keywords: coordination polymer; characterization; optical property 1. Introduction Coordination polymers (CPs) consisting of organic ligands and metal ions have attracted an upsurge in research during the past decades, due to their charming structures and their possibly applied domain of luminescence [1–4], gas adsorption/separation [5,6], proton conductivity [7], chemical separations [8], catalysis [9], and so on.
    [Show full text]
  • Crown Ethers and Their Alkali Metal Ion Complexes As Assembler Groups in Uranyl–Organic Coordination Polymers With
    Crown Ethers and Their Alkali Metal Ion Complexes as Assembler Groups in Uranyl–Organic Coordination Polymers with cis -1,3-, cis -1,2-, and trans -1,2-Cyclohexanedicarboxylates Pierre Thuéry, Youssef Atoini, Jack Harrowfield To cite this version: Pierre Thuéry, Youssef Atoini, Jack Harrowfield. Crown Ethers and Their Alkali Metal Ion Complexes as Assembler Groups in Uranyl–Organic Coordination Polymers with cis -1,3-, cis -1,2-, and trans - 1,2-Cyclohexanedicarboxylates. Crystal Growth & Design, American Chemical Society, In press, 18 (5), pp.3167-3177. 10.1021/acs.cgd.8b00266. cea-01759418 HAL Id: cea-01759418 https://hal-cea.archives-ouvertes.fr/cea-01759418 Submitted on 6 Apr 2018 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Crown Ethers and their Alkali Metal Ion Complexes as Assembler Groups in Uranyl–Organic Coordination Polymers with cis -1,3-, cis -1,2- and trans -1,2-Cyclohexanedicarboxylates Pierre Thuéry* ,† Youssef Atoini ‡ and Jack Harrowfield*,‡ †NIMBE, CEA, CNRS, Université Paris-Saclay, CEA Saclay, 91191 Gif-sur-Yvette, France ‡ISIS, Université de Strasbourg, 8 allée Gaspard Monge, 67083 Strasbourg, France ABSTRACT: Alkali metal cations (Na +, K +) and crown ether molecules (12C4, 15C5, 18C6) were used as additional reactants during the hydrothermal synthesis of uranyl ion complexes with cis /trans -1,3-, cis -1,2- and trans -1,2- cyclohexanedicarboxylic acids ( c/t-1,3-chdcH2, c-1,2-chdcH2 and t-1,2-chdcH2, respectively, the latter as racemic or pure (1 R,2 R) enantiomer).
    [Show full text]
  • Coordination Polymers, Metal-Organic Frameworks and the Need for Terminology Guidelines
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE Accepted manuscript: CrystEngComm, 2012,14, 3001-3004 provided by Chalmers Publication Library DOI: 10.1039/C2CE06488J, http://pubs.rsc.org/en/content/articlelanding/2012/ce/c2ce06488j Coordination Polymers, Metal-Organic Frameworks and the Need for Terminology Guidelines Stuart R. Battena, Neil R. Champnessb, Xiao-Ming Chenc, Javier Garcia-Martinezd, Susumu Kitagawae, Lars Öhrströmf*, Michael O’Keeffeg, Myunghyun Paik Suhh and Jan Reedijki,j Coordination Polymers (CP) and Metal-Organic Frameworks (MOF) are among the most prolific research areas of inorganic chemistry and crystal engineering in the last 15 years, and yet it still 5 seems that consensus is lacking about what they really are, or are not. Background Nomenclature and terminology should always create added value. They are tools to incorporate new results into the greater weave of science and enable us to go from the specific to the general. New terminology should also help us to constructively discuss new compounds, 10 materials and phenomena without having to proceed through endless preambles of definitions. When two or more sub-disciplines of science find themselves preparing and analysing similar kinds of new materials, an ad hoc terminology often develops from different viewpoints and may not naturally converge into a self-consistent and logical result. This dual situation occurs for Coordination Polymers (CP)1 and Metal-Organic Frameworks 2 15 (MOF) , compounds generated in interdisciplinary research fields with their origins in solid state, inorganic and coordination chemistry that have expanded rapidly during the last 15 years. The diversity in both focus and scientific basis of the researchers involved has lead to numerous terminology suggestions and practices for this class of compounds and of several subgroups within them;3 additionally, a disquieting number of acronyms are also in use for these materials.
    [Show full text]
  • One Dimensional Coordination Polymers Based on Bridging N,N Donor Ligands
    One Dimensional Coordination Polymers Based on Bridging N,N Donor Ligands Der Naturwissenschaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg zur Erlangung des Doktorgrades Dr. rer. nat. vorgelegt von Nico Fritsch aus Forchheim Als Dissertation genehmigt von der Naturwissen- schaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg Tag der mündlichen Prüfung: 13. Juni 2014 Vorsitzender des Promotionsorgans: Prof. Dr. Johannes Barth Gutachter: Prof. Dr. Nicolai Burzlaff Prof. Dr. Julien Bachmann Die vorliegende Arbeit entstand in der Zeit von Juni 2011 bis März 2014 im Department für Chemie und Pharmazie (Lehrstuhl für Anorganische und Metallorganische Chemie) der Friedrich-Alexander-Universität Erlangen-Nürnberg unter der Anleitung von Prof. Dr. Nicolai Burzlaff. Teile dieser Dissertation wurden bereits veröffentlicht: “trans-1,2-Bis(N-methylimidazol-2-yl)ethylene: Towards Building Blocks of 2D Fabrics and MML-Type 2D Molecular Strands”, N.V. Fischer, M. S. Alam, I. Jum´h, M. Stocker, N. Fritsch, V. Dremov, F.W. Heinemann, N. Burzlaff, P. Müller, Chem. – Eur. J., 2011, 17, 9293-9297. “Battlement-shaped 1D coordination polymer based on bis(N-methylimidazole-2yl)butadiyne ligand”, T. Waidmann, N. Fritsch, J. Tucher, M. Rudolf, F. Glaser, D.M. Guldi, N. Burzlaff, CrystEngComm, 2013, 10157-10160. – Reproduced by permission of The Royal Society of Chemistry. You can´t always get what you want. But if you try sometimes you might find, You get what you need. (Sir Mick Jagger) Table of contents 1! GENERAL INTRODUCTION ............................................................................................ 1! 1.1! From metal organic frameworks to 1D coordination polymers ........................................... 2! 1.2! Different concepts of molecular wires .................................................................................... 5! 1.2.1! Organic based molecular wires ..........................................................................................
    [Show full text]
  • A Supramolecular Coordination Polymer Derived Electrocatalyst for Oxygen Evolution Reaction
    A Supramolecular Coordination Polymer Derived Electrocatalyst for Oxygen Evolution Reaction Chi Zhang,a Chen Zhang,b Yunchao Xie,a Xiaoqing He,c Tommi White,c d Derek Demaree,e Mark H. Griep,e Jerry L Atwood*b and Jian Lin*a a. Department of Mechanical & Aerospace Engineering, University of Missouri, Columbia, Missouri 65211, United States. E- mail: [email protected] b. Department of Chemistry, University of Missouri, Columbia, Missouri 65211, United States. E-mail: [email protected] c. Electron Microscopy Core Facility, University of Missouri, Columbia, MO 65211, United States d. Department of Biochemistry, University of Missouri, Columbia, MO 65211, United States e. U.S. Army Research Laboratory, 4600 Deer Creek Loop, Aberdeen Proving Groun, Maryland 21005, United States An iron oxide decorated nickel iron alloy nanoparticle/porous graphene hybrid exhibits high electrocatalytic activity and excellent durability toward oxygen evolution reaction (OER). It displays a LOW overpotential of 274 mV at 10 mA/cm2, and low Tafel slope of 37 mV/dec, showing a superior performance to the state-of-the-art RuO2 OER electrcatalyts. Scanning electron microscopy (SEM) was performed to characterize the morphology and structure. Fig. 1b shows that the nanoparticles are well dispersed on the surface of the LIG sheets. The corresponding elemental mapping confirms the existence of the C, O, Fe, and Ni elements and their uniform dispersion. High-resolution TEM (HRTEM) was further performed to investigate the nanostructures in more details. The HRTEM image (Fig. 1d) reveals well-resolved lattice fringes with interplanar distances of 0.205 nm, 0.290 nm and 0.364 nm, of Fe3O4 and (002) plane of graphene, respectively.
    [Show full text]
  • Synthesis and Crystal Structure of a New Calcium-Containing Trimesate Coordination Polymer: [Ca3(Btc)2(H2O)12]∞
    Synthesis and crystal structure of a new calcium-containing trimesate coordination polymer: [Ca3(btc)2(H2O)12]1. Magatte Camara, Carole Daiguebonne, Olivier Guillou, Albert Manga Badiane, Insa Badiane, Saïbatou Yague, Florence Le Dret To cite this version: Magatte Camara, Carole Daiguebonne, Olivier Guillou, Albert Manga Badiane, Insa Badiane, et al.. Synthesis and crystal structure of a new calcium-containing trimesate coordination polymer: [Ca3(btc)2(H2O)12]1.. Journal de la Société Ouest-Africaine de Chimie, Société Ouest-Africaine de Chimie, 2013, 035, pp.57-63. hal-01074624 HAL Id: hal-01074624 https://hal.archives-ouvertes.fr/hal-01074624 Submitted on 15 Oct 2014 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Journal de la Société Ouest-Africaine de Chimie J. Soc. Ouest-Afr. Chim. Code Chemical Abstracts : JSOCF2 Cote INIST (CNRS France) : <27680> ISSN 0796-6687 18èmeAnnée, Juin 2013, N° 035 Site Web: http://www.soachim.org J. Soc. Ouest-Afr. Chim. (2013) 035 ; 57 - 63 Synthesis and crystal structure of a new calcium-containing trimesate coordination polymer: [Ca3(btc)2(H2O)12]∞. Magatte Camaraa*, Carole Daiguebonneb,c, Olivier Guilloub,c, Albert Manga Badianea, Insa Badianea, Saïbatou Yaguea, Florence Le Dretb,c.
    [Show full text]
  • Mossbauer Spectroscopic Studies of Complexes of Fe(III) with Nitrogen Containing Polymers
    Polymer Journal, Vol. 23, No. 4, pp 339~342 (1991) NOTES Mossbauer Spectroscopic Studies of Complexes of Fe(III) with Nitrogen Containing Polymers E. A. BEKTUROV, S. E. KUDAIBERGENOV, G. S. KANAPYANOVA, S. S. SALTYBAEVA, A. I. SKUSHNIKOVA, A. L. PAVLOVA, and E. S. DoMNINA * Institute of Chemical Science, Kazakh SSR Academy of Sciences, Alma-Ata 480100, Krasin Str. 106, USSR * Institute of Organic Chemistry Siberian Branch of Academy of Sciences of the USSR, Irkutsk, USSR (Received July 30, I 990) KEY WORDS Nitrogen Containing Polymers / Complex Formation / Mossbauer Spectroscopy / Coordination polymer compounds have EXPERIMENT AL been successfully used in various catalytic processes such as hydrogenation, oxidation, P2VPy, P2M5VPy, and P4VPy were synthe­ hydroformylation, polymerization, isomeriza­ sized by the radical polymerization of mono­ tion, etc. 1 Nitrogen containing polymers are mers in methanol at 333 K in presence of interesting polymer ligands that function as azobisisobutyronitrile (AIBN) as initiator. 8 supports in catalysis. Copolymers based on VI and VP were Complex formation ability of nitrogen synthesized by radical copolymerization in containing polymers in relation to the transi­ ethanol at 333 Kin the presence of AIBN. All tion metal ions is due to the presence of polymers and copolymers were purified by primary, secondary and tertiary aminogroups fractional precipitation. The compositions of which are able to form donor-acceptor copolymers were determined by IR spectros­ bonds. 2 - 7 The structures of coordination copy9 and by elemental analysis. PVI with compounds influence on the catalytic activity molecular weight 16 x l 03 and commercial of polymer-metal complexes. sample of PVP with molecular weight 5.6 x 10 5 In the present paper the results of an were used.
    [Show full text]
  • A New Calcium(II) Coordination Polymer Based on a Μ2-Bridging Tridentate 4-Nitrobenzoate
    Indian Journal of Chemistry Vol. 51A, March 2012, pp. 435-443 A new calcium(II) coordination polymer based on a µ2-bridging tridentate 4-nitrobenzoate Bikshandarkoil R Srinivasana, *, Santosh Y Shetgaonkara, Manav Saxenab & Christian Nätherc aDepartment of Chemistry, Goa University, Goa 403 206, India Email: [email protected] bDepartment of Chemistry, Indian Institute of Technology, Kanpur, 208 016 India cInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth Strasse 2, D-24118 Kiel, Germany Received 17 September 2011; revised and accepted 16 January 2012 Reaction of a heptacoordinated Ca(II) compound [Ca(H2O)4(4-nba)2] (4-nba = 4-nitrobenzoate) with 3,5-dimethyl- pyrazole (dmp) leads to the formation of an eight coordinated Ca(II) compound, [[Ca(H2O)2(4-nba)2]·2dmp]n, containing two coordinated water molecules, two unique 4-nba ligands and two free dmp molecules in the lattice. The µ2-bridging tridentate binding mode of the unique 4-nba ligands results in the formation of a one-dimensional (1-D) coordination polymer. The title compound exhibits enhanced fluorescence emission. An analysis of the six different bridging binding modes of the 4-nba ligand in twenty two different structurally characterized 4-nitrobenzoate compounds is described. Keywords: Coordination chemistry, Calcium, 4-Nitrobenzoates, 3,5-Dimethylpyrazole, Coordination polymers, Metal organic frameworks Coordination polymers (CPs) also known as metal differing dimensionalities can be constructed. For the organic frameworks (MOFs) have attracted much oxophilic s-block metals, carboxylic acids are useful attention because of their topology and applications in linkers for the construction of coordination polymers catalysis, adsorption (gas storage), separation and as the metals can be linked into an extended chain luminescence1-3.
    [Show full text]
  • Synthesis and Characterization of a New Strontium(II) Coordination Polymer Based on a Μ2-Tridentate Bridging Zwitterionic Glyci
    Published in: Journal of Coordination Chemistry: 64(13); 2011; 2274-2283. Synthesis and characterization of a new strontium(II) coordination polymer based on a µ2-tridentate bridging zwitterionic glycine aS. Natarajan *, aJ. Kalyana Sundar, bS. Athimoolam, cBikshandarkoil R. Srinivasan a *School of Physics, Madurai Kamaraj University, Madurai 625 021, India b Department of Physics, University College of Engineering Nagercoil, Anna University of Technology Tirunelveli, Nagercoil 629 004, India c Department of Chemistry, Goa University, Goa 403206, India Abstract The synthesis and characterization of a new Sr(II) coordination polymer [Sr(H 2O)(H- gly)2Cl2]n 1 (H-gly = glycine) is described. Compound 1 crystallizes in the centrosymmetric orthorhombic space group Pcnb and its structure consists of a central Sr(II) ion, a terminal water, a unique zwitterionic glycine and a chloride ion. The central metal is nine coordinated and is bonded to six oxygen atoms from four different bridging H-gly ligands, two symmetry related chloride ions and a terminal water. The µ2-tridentate bridging nature of the zwitterionic glycine results in the formation of a one dimensional coordination polymer with a Sr···Sr separation of 4.560 Å across the chain. The chloride, H-gly and the coordinated water are involved in five varieties of H-bonding interactions. A comparative study of the structural chemistry of several alkaline-earth glycine compounds is described. Keywords: Coordination polymer; strontium; glycine; zwitterion. 1 REVISED MANUSCRIPT GCOO-2011-0182 1. Introduction Coordination polymers (CPs) also known as metal organic frameworks (MOFs) have attracted much attention because of their topology and applications in catalysis, adsorption (gas storage), separation, luminescence [1-3].
    [Show full text]