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Supramolecular Chemistry of Functionalized Terpyridines

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Supramolecular Chemistry of Functionalized Terpyridines SUPRAMOLECULAR CHEMISTRY OF FUNCTIONALIZED TERPYRIDINES A Dissertation Presented to The Graduate Faculty of the University of Akron In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Ibrahim Eryazici December, 2007 SUPRAMOLECULAR CHEMISTRY OF FUNCTIONALIZED TERPYRIDINES Ibrahim Eryazici Dissertation Approved: Accepted: _________________________ _________________________ Advisor Department Chair Dr. George R. Newkome Dr. Mark D. Foster _________________________ _________________________ Committee Member Dean of the College Dr. Judit E. Puskas Dr. Stephen Cheng _________________________ _________________________ Committee Member Dean of the Graduate School Dr. Li Jia Dr. George R. Newkome _________________________ _________________________ Committee Member Date Dr. Ernst von Meerwall _________________________ Committee Member Dr. Jun Hu ii ABSTRACT Highly ordered, regularly repeating molecular architectures, constructed via self- assembly techniques, have gained importance over the last three decades due to their potential utilitarian applications. A key construction strategy has relied on the synthesis of specific building blocks capable of forming “higher-ordered” stable structures that have useful properties that can be used as molecular and supramolecular devices. To this end, mono and bis(terpyridine) ligands have been widely used because of their well known photochemical and electronic properties, as well as their ability to facilitate directed, metal-mediated self-assembly. However, limited accessibility to unsymmetrically functionalized terpyridines has restricted their potential use in the construction of more complex infrastructures. For this purpose, methyl-, methoxy- carbonyl- and cyano-substitution patterns on the 4,4''-positions of 4'-arylterpyridine were chosen since these functionalities afforded simple routes to a variety of useful substituted building blocks for higher-ordered supramacromolecular architectures. Single crystal X- ray studies of these terpyridines revealed that molecules of the diester terpyridine (approximately coplanar) are stacked by the overlap of the central pyridine rings in consecutive layers with mean interplanar distances of 3.4 Å (π – π interactions) in the solid state. Moreover, functionalized bis(terpyridine) ligands were achieved via the Kröhnke method and Pd(0) coupling strategy using either 1,3-toluenylbisboronic acid or 1,3-diethynyltoluene with meta- or para-I or Br-phenylterpyridines. iii A dinuclear tetracationic Fe(II) complex was prepared via metal-directed self- assembly. The chair-like molecular architecture was primarily characterized by X-ray crystallography, mass spectroscopy (ESI-MS), as well as 1H NMR, UV-vis, and CV experiments. Crystal packing of this metallomacrocycle revealed that it formed channels that encapsulated water and MeCN. The low temperature 1H NMR studies suggested that tpy-Fe-tpy moieties in the dimer were interlocked and resembled a spur gear relationship. Surprisingly, dinuclear and trinuclear metallomacrocycles were formed when 1,3- bis(2,2';6',2''-terpyridine-4'-phen-3-ylethynyl)toluene was treated with equimolar amount of Ru(II) that was confirmed by MALDI-TOF mass and NMR spectroscopy. The construction of a heteronuclear (Ru4Fe2) hexameric metallomacrocycle with methyl- and carbonyl-functionalized bis(terpyridyl) moieties was achieved by Pd(0) coupling strategy for potential solar cell applications and supramolecular aggregation of the resulting hexamers through H-bonding. Carboxylic acid functionalized mono- and dinuclear homo- and heteroleptic Ru(II) precursors were also prepared for the same purposes. The single crystal X-ray structure of a homoleptic Ru(II) complex with tetra- ethoxycarbonyl and di(iodo) groups revealed short iodo-carbonyl interactions. iv DEDICATION I dedicate this work to my wonderful parents, Omer and Ayse Eryazici, and my lovely wife, Paula Eryazici, who provided and supported me all these years. v ACKNOWLEDGEMENTS Firstly, I want to thank Dr. Newkome for his infinite patience with me and his teachings about research and chemistry. I am very thankful for his guidance that lead me to learn to think outside the box. I am just hoping that I have learned a little bit of his endless knowledge and experience in science and research. I also thank Dr. Moorefield for his help in the lab. I thank Dr. Wang for his expertise on growing single crystal and Dr. Durmus and Dr. Panzner for their effort in crystal structure analysis. I also thank all my colleagues who I have worked with six years for their academic discussions. Lastly, I want to thank my parents who sacrificed so much for me to be here and I thank my wife for her endless support for my work. vi TABLE OF CONTENTS Page LIST OF TABLES………...….………………………………………………...…...........xi LIST OF FIGURES….…………………………………………………………...….......xii LIST OF SCHEMES.......................................................................................................xxv CHAPTERS I SYNTHESIS OF TERPYRIDINES, THEIR SUPRAMOLECULAR CONSTRUCTS AND BIOLOGICAL APPLICATIONS BASED ON THEIR SQUARE PLANAR COMPLEXES………...……...………….1 1.1 Introduction……………………………………………………………………..1 1.2 2,2':6',2''-Terpyridine Synthesis and Functionalization Strategies……………..4 1.2.1 Ring Assembly Methods…………………………………………………...4 1.2.1.1 Kröhnke method………………………………………………………4 1.2.1.2 Potts Method………………………………………………………….6 1.2.1.3 Jameson Method……………………………………………………...7 1.2.1.4 Adrian Method………………………………………………………..8 1.2.1.5 Sauer Method………………………………...……………………….9 1.2.2 Cross-Coupling Methods…………………………………………………10 1.3 Square Planer Terpyridine Transition Metal Complexes……………………...11 1.3.1 Chemistry and Properties…………………………………………………12 1.3.1.1 Synthesis………………………………………………………….....12 vii 1.3.1.2 Characterization……………………………………………………..18 1.3.1.3 Single Crystal X-ray Structures and Their Molecular Packing……..21 1.3.1.4 Dimerization and Its Constant (KD)…………………………………27 1.3.1.5 Photophysical Properties…………………………………………….27 1.3.1.6 Electrochemical Properties………………………………………….33 1.3.1.7 Fluxionality………………………………………………………….34 1.3.2 Mononuclear Terpyridine Complexes…………………………………....38 1.3.2.1 Luminescent Pt-Terpyridine Complexes……………………………38 1.3.2.2 Molecular Packing and Induced Self-assembly……………………..41 1.3.2.3 Molecular Sensors and Switches……………………………………47 1.3.2.4 Photocatalytic Activities…………………………………………….58 1.3.2.5 Miscellaneous Applications…………………………………………65 1.3.3 Metallo-Supramolecular Terpyridine Architectures……………………...71 1.3.3.1 Dyads and Triads……………………………………………………72 1.3.3.2 Supramolecular Self-Assemblies……………………………………88 1.3.3.3 Molecular Recognition by Host-Guest Interaction………………….92 1.3.3.4 Multimetallic Peptide Scaffolds……………………………………..99 1.3.4 Biological Activities………………………………………………….....102 1.3.4.1 DNA Intercalation………………………………………………….102 1.3.4.1.1 UV-vis Spectroscopy Analysis and Binding Modes………….103 1.3.4.1.2 Viscosity and Thermal Denaturation…………………………107 1.3.4.1.3 Induced Circular Dichroism…………………………………..109 1.3.4.1.4 Competitive Fluorescence Spectroscopy……………………..110 viii 1.3.4.1.5 Closed Circular DNA…………………………………………112 1.3.4.1.6 Stereochemical Changes in DNA…………………………….113 1.3.4.1.7 Site Specific Intercalation…………………………………….115 1.3.4.1.8 Other Mononuclear Intercalators……………………………..117 1.3.4.1.9 Multinuclear Intercalators…………………………………….120 1.3.4.2 Covalent Binding to Biomolecules………………………………...126 1.3.4.3 Labeling Biomolecules…………………………………………….132 1.3.4.4 Cytotoxicity………………………………………………………...138 1.3.4.4.1 Chemotheraputic Agents……………………………………...139 1.3.4.4.2 Radiotheraputic agents………………………………………..148 1.4 Conclusion………………………………………………………….………..149 II SYNTHESIS AND SINGLE CRYSTAL X-RAY CHARACTERIZATION OF 4,4''- FUNCTIONALIZED 4'-(4-R-PHENYL)-2,2':6',2''-TERPYRIDINES…...................................................150 2.1 Introduction……………..................................................................................150 2.2 Results and Discussion…………………..………………………..................152 2.3 Conclusion………………………………….…………………..…................165 2.4 Experimental Section……………………….…………………..…................166 III MISCELLANEOUS BY-PRODUCTS OF KRÖHNKE TERPYRIDINE SYNTHESIS………..………….........…………..…….........…...182 3.1 Introduction……………..................................................................................182 3.2 Results and Discussion….…………..……………………….........................183 3.3 Conclusion………………………………...….…………………..….............187 3.4 Experimental Section……...………………….…………………..….............187 ix IV DESIGN, CHARACTERIZATION AND X-RAY STRUCTURE OF AN INTERLOCKED DINUCLEAR CHAIR-LIKE METALLOMACROCYCLE...................................................................................191 4.1 Introduction……………..................................................................................191 4.2 Results and Discussion….………………….……………………..................193 4.3 Conclusion………………………………………………………..….............199 4.4 Experimental Section……………………………………………..….............199 V ONE POT SELF ASSEMBLY OF DI- AND TRI-NUCLEAR METALLOMACROCYLES AND THEIR MALDI-TOF ANALYSIS..…….…..204 5.1 Introduction……………..................................................................................204 5.2 Results and Discussion….………...……..………………………..................206 5.3 Conclusion………………………………….………...…………..….............213 5.4 Experimental Section……………………………………………..….............214 VI CONSTRUCTION OF A HEXANUCLEAR MACROCYLE BY A COUPLING STRATEGY FROM 4,4''-FUNCTIONALIZED BIS(TERPYRIDINES)…………………………………………………….............220
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