SCHOOL OF CHEMISTRY CARDIFF UNIVERSITY Ca r d if f UNIVERSITY PRIFYSGOL CaeRDY|§> Synthesis and crystal structures of phthalocyanine derivatives containing bulky phenyloxy substituents Thesis submitted for the degree of Doctor of Philosophy by: Caterina Gavina Grazia Bezzu Supervisor: Neil B. McKeown 2009 UMI Number: U585182 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. Dissertation Publishing UMI U585182 Published by ProQuest LLC 2013. Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code. ProQuest LLC 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106-1346 Declaration This work has not previously been accepted in substance for any degree and is not concurrently submitted in candidature for any degree. Signed. .. f&iMcw (candidate) STATEMENT 1 This thesis is being submitted in partial fulfilment of the requirements for the degree of Doctor of Philosophy. Signed.. J ^ . £ 3 .^t.. (candidate) Date. .Q £ /.V.S./.Q 3............ STATEMENT 2 This thesis is the result of my own independent work/investigation, except where otherwise stated. Other sources are acknowledged by explicit references. S i g n e d . ... (candidate) STATEMENT 3 I hereby give consent for my thesis, if accepted, to be available for photocopying and for interlibrary loan, and for the title and summary to be made available to outside organisations. S i g n e d . olq... 5^. .£7 .../S fcM tu. (candidate) Date.. Q . f. / I To my Family II Acknowledgments Firstly I would like to thank my supervisor Professor Neil Mckeown for his constant guidance, patience and support throughout the course of my PhD. A particular acknowledgement goes to Dr Madeleine Helliwell for the many days spent in Daresbury Laboratory collecting data and for solving the X-ray crystal structures which have been fundamental for this thesis work. I would also like to thank Dr John Warren for his precious help in station 9.8 at Daresbury Laboratory. Also, many thanks to everybody in my group, in particular to Dr Kadhum Msayib for his help since the beginning of my PhD, and to everybody in lab. 1.107. Many thanks to Vanesa and Manuel with who I have shared this experience since the very start and for all the beautiful moments spent together. Special thanks to all Sardinian people (Antonio R., Antonio F., Deborha, Alessandra, Gianluca, Sergio, Simona, Maurizio) who made me feel home and in particular to Caterina for have become one of my best friends and to all the other people in the old crew (Vincenzo, Adrien, Eugene, Dave, Txell, Veronica, Niek, Paula, Anabel, Dirk, Soraya, Paola, Elisenda, Nicholas, Damien, Massimo, Sabine) for made my life in Cardiff more enjoyable. Infinite thanks to my family for being always close to me even from far away. Finally, immense gratitude goes to Lino who has been always on my side, supporting me with endless patience and love and without whom I would have not been able to accomplish all of this. Ill Preface Abstract The planar extended shape of the phthalocyanine macrocycle results in a strong tendency of its derivatives to form densely packed co-facial aggregates. The strategy to avoid co-facial self-association that forms the basis of this thesis involves the use of substituents that can introduce severe steric crowding adjacent to the phthalocyanine core. Previous work showed that the introduction of 2 ,6 -di-/j 0 -propylphenoxy groups on the peripheral positions of the phthalocyanine seems to be perfect for this purpose. Of particular interest is zinc octa(2,6-di-/$o-propylphenoxy) phthalocyanine (PclZn), which forms a remarkable cubic crystal structure, containing interconnected solvent-filled voids 2 nm across. The aim of the research programme was to investigate the crystal forming properties of related phthalocyanine derivatives containing different metal cations and bulky phenoxyl substituents. A range of metal cations were introduced into 2,3,9,10,16,17,23,24-octa(2\6’-di-/so- propylphenoxy) phthalocyanine (Pci) to establish which, if any, were compatible with the formation of the nanoporous cubic crystal observed for the zinc derivative. It was found that any metal capable of binding to a ligand at its axial site formed the cubic crystal including metals of primary catalytic relevance such as cobalt, iron, manganese and ruthenium. Single crystal X-ray diffraction studies demonstrated the exchange of axial ligands to confirm the interconnectivity of the nanovoids, which is essential for the potential exploitation of these molecules in heterogeneous catalysis. Of particular interest is the introduction of bidentate ligands, which act as structural wall ties that bind metals between cubic subunits. Since loss of crystallinity occurs after removal of the guest solvent from the cubic clathrates, the introduction of substituents at the 4-position of the phenoxy groups was also investigated in order to induce stronger dipole-dipole (e.g., R = Br, Cl, CN, OMe) or hydrogen bond interactions (e.g., R = OH), which might stabilise the crystal structure. Unfortunately, these derivatives formed non-cubic crystals, although in each case solvent was included within the structure to form novel clathrates. IV Preface Abbreviations A Angstrom APCI Atmospheric pressure chemical ionisation aq aqueous bipy 4,4'-bipyridyl Bislm 1 ,2 -bisimida-zol - 1 -ylethane br Broad calc. Calculated DABCO 1,4-diazabicyclo[2.2.2]octane DBN 1,5-diazabicyclo[4.3.0]non-5-ene DBU 1,8-diazabicyclo[5.4.0]undecene DCM Dichloromethane 1 ,6 -diahex 1 ,6 -diaminohexane dimepy 3,5-dime thylpyridine DMAc N,N-Dimethylacetamide DMAE N,N-dimethylaaminoethanol DMF A,A-Dimethylformamide DMSO Dimethyl sulphoxide El Electron Impact ES Electrospray Et Ethyl Et20 Diethylether EtOAc Ethyl acetate EtOH Ethanol g Grams GPC Gel Permeation Chromatography h Hour/s HRMS High Resolution Mass Spectrometry Hz Hertz Im imidazole IR Infra Red IUPAC International Union of Pure and Applied Chemistry J Coupling constant (in Hz) lit. Literature LRMS Low Resolution Mass Spectrometry m Multiplet MALDI Matrix-assisted laser desorptio/ionisation Me Methyl Melm 1 -methyl imidazolyl MeOH Methanol mmol Millimole(s) V Preface MOF Metal Organic Framework MOP metal-organic polyhedra M.p. Melting point nm nano meters NMIm N-methylimidazole NMP N-methyl pyrrolidone NMR Nuclear Magnetic Resonance NOESY Nuclear Overhauser Enhancement Spectroscopy OBu Butoxide Pc Phthalocyanine Ph Phenyl Phic 1,4-phenyleneisocyanide pic 4-picoline PIM Polymers of Intrinsic Microporosity py pyridine q quartet r.t. room temperature s singlet t triplet t-Bu tert butyl t- BuNC te/Y-butylisocyanide t-Bupy /-butylpyridine THF Tetrahydrofuran TLC Thin Layer Chromatography TMS Trimethylsilyl TpyP 5,10,15,20-tetra^’-pyridylporphyrin UV Ultraviolet V volume XRD X-ray diffraction VI Preface Table of contents Declaration.......................................................................................................I Acknowledgments ........................................................................................Ill Abstract.........................................................................................................IV Abbreviations................................................................................................. V Table of contents ........................................................................................ VII 1. Introduction ................................................................................................ 1 1.1 History of phthalocyanine research............................................................................... 1 1.2 Phthalocyanine synthesis...................................................................................................2 1.2.2 Metal free phthalocyanine........................................................................................... 2 1.2.3 Metal phthalocyanine....................................................................................................3 1.3 Phthalocyanine applications as materials..................................................................... 4 1.4 Supramolecular organization of phthalocyanines.......................................................5 1.5 Porphyrins and Phthalocyanines in catalysis as mimics of cytochrome P-450 ....8 1.5.1 Cytochrome P-450 ........................................................................................................ 8 1.5.2 Porphyrins as mimic models of cytochrome P-450 .................................................. 8 1.5.3 Phthalocyanines as mimic models of cytochrome P-450 ...................................... 12 1.6 Microporous organic materials .....................................................................................14 1.6.1 Metal-organic frameworks ......................................................................................... 14 1.6.2 Porphyrin clathrates.................................................................................................... 17 1.6.3 Phthalocyanines clathrates.........................................................................................20 1.7 Aims and objectives........................................................................................................