The Research Of TTF Carboxylic Charge Transfer Compounds With Photoelectric Properties

Due to their unique donor and redox properties, tetrathiafulvalene(TTF) and its derivatives have stimulated great interest for a long time and have been used in many areas,such as supramolecular chemistry, conductor, semiconductor, superconductor materials,biological sensors, chemical sensors and macrocyclic chemistry. In comparison with the extensive research on other TTF derivatives, the study of TTF–carboxylic compounds has not been extensively carried out and has mainly been focused on supramolecular assembly and crystal structures. The research on charge transfer of TTF–carboxylic compounds is relatively fewer. In this thesis, TTF–carboxylic derivatives are assembled with functionality acceptors and transition metal ions. It mainly includes the following contents:In introduction, properties and research progress of TTF and its derivatives were reviewed briefly. The applications of TTFs in molecular devices and photo–voltaic materials were summarized. Research progress of TTF–carboxylic derivatives in compositing functional materials and constructing metal organic frameworks was introduced. Besides, the applications in optical, electrical and solar cell fields of MVs and charge transfer compounds were reviewed briefly. Finally, the significance and the main contents of the thesis are introduced.In chapter 2, we synthesized four {[cation]n+·[TTFs]n–} IPCT complexes:(MV)2[Li4(L)2(H2O)6](1), {(MV)(L)[Na2(H2O)8]·4H2O}n(2),{(MV)[Mn(L)(H2O)2]?2H2O}n(3), and {(MV)[Mn(L)(H2O)2]}n(4) based on TTF tetracarboxylate metal coordinated anion and [MV]2+ cation. X–ray structural analysis of the four compounds reveals that TTF moiety and [MV]2+ form a regular mixed–stack arrangement in alternating DADA fashion. By solid ultraviolet spectrum, ESR and magnetic measurements, combined with molecular packings, we studied the charge–transfer phenomenon of these four complexes. Compounds 2, 3, and 4 show aneffective and repeatable photocurrent response. The relationship between photocurrent response intensity and molecular structures was explained. Moreover, photocurrent generation diagram including the electron flow was set forth.In chapter 3, we synthesized three compounds:(Dmbpe)2(TTF–TC)·10H2O(5),(Dmbpe)(TTF–TC)H2(6),and [Mn(H2O)6](MQ)2(TTF–TC)(7) based on Na4(TTF–TC)with [Dmbpe]2+ and [MQ]+, derivatives of [MV]2+, and measured the crystal structures of these compounds. Molecular packings and optical properties were discussed. The ESR measurements indicate that charge transfer occurs in these complexes. Photocurrent response properties of these compounds were investigated. And we further prepared four self–assembled molecular films: [DCn MV]Br2–Na4(TTF–TC)(n=4, 8, 12, 16),based on Na4(TTF–TC) and MVs. We investigated the photocurrent response properties of[DCn MV]Br2–Na4(TTF–TC)(n=8, 12, 16), and found that the compound with a longer alkane chain has a smaller photocurrent.In chapter 4, we synthesized two compounds: {[Fe(H2O)4]2[TTF–TC]}·4H2O(8),and [Fe(H2O)6](TTF–TC)H2·2H2O(9) based on Li4(TTF–TC) and transition metal ion Fe(II). Crystal structures were determined by X–ray diffraction. We found that red compound 8 can transform into 9 at solid phase. PXRD and SEM were measured to prove the process. The optical properties, electrochemical properties and photocurrent response of compounds 8 and 9 were discussed.