Synthesis And Properties Of Metal Complexes Based On Conjugated Multi-Sulfur Containing Ligands

Metal bis(dithiolene)complexes can be used as selective near-infrared absorption materials owing to their extensive ?-conjugation delocalization systems and the relatively small HOMO-LUMO gaps.Tetrathiafulvalene(TTF)and its derivatives have been widely applied to the development of molecular conductorors,superconductors and the construction of supramolecular compounds,due to their reversible redox electrochemical activities.In this dissertation,we design and synthesize a series of functional complexes based on p-conjugated multi-sulfur containing ligands,such as multi-sulfur dithiolenes and TTF skeleton as the center,by taking the selecting different conjugated coordinatio n groups to connect with them.Their photophysical and electrochemical properties were also studied.1.Four new nickel complexes containing benzo-groups based on the multi-sulfur dithiolene ligands,(n-Bu4N)[N i(Lx)2](L1 = benzo[b][1,4]dithiin-2,3-dithiolate,1;L2 = 6,7-dimethylbenzo[b][1,4]dithiin-2,3-dithiolate,2;L3 = 6,7-dimethoxylbenzo[b][1,4]dithiin-2,3-dithiolate 3;L4 = 5,6,7,8-tetrafluorobenzo[b][1,4]dithiin-2,3-dithiolate 4)have been synthesized.The structures of all new complexes have been determined by X-ray crystallography.In crystal state,nickel bis(dithiolene)anions of complexes 1–4 all show chair-like configurations.Intermolecular nonclassical hydrogen-bond between [n-Bu4N]+ cations and nickel bis(dithiolene)anions or nickel bis(dithiolene)anions are also found in 2–4.The relationship between the electron donating/withdrawing abilities of the substituents and the wavelength of the characteristic bands is observed from UV-vis-NIR absorption spectra,and further explained by the TD-DFT calculations and MO energy analysis.The electrochemistry of complexes 1–4 and magnetic properties were also determined and analyzed.The results confrmed that their electrochemical properties and electronic transition band could be tuned via modifying different functional groups.2.Three new Mn(II)-based CPs,{[Mn Cl2][TTF(py)4]·4(CH2Cl2)·(CH3OH)}n(5),{[Mn(N3)][TTF(py)4]·(Cl O4)·2(CHCl3)·(CH3OH)}n(6),{[Mn(dca)2][TTF(py)4]0.5·(CH3OH)}n(7)(dca = dicyanamide),have been self-assembly from the redox-active tetra(4-pyridyl)-tetrathiafulvalene ligand with Mn(II)salts comprising different anions,namely,Cl?,N3?,and N(CN)2?.The structures of all new complexes have been determined by X-ray crystallography.Structural analysis shows that the anions play an important role in governing the structures of the CPs.Complexes 5–7 present different and interesting two-dimensional or three-dimensional structures.We also investigated the magnetism,conductivity and solid-state electrochemical behavior of the three CPs.The magnetic measurement shows that the three complexs are all antiferromagnetic.In addition,the solid-state electrochemical studies on the three complexes revealed that the CPs retained the redox activity of the TTF moiety.The results showed that the incorporation of redox-active ligands into CPs may be an effective way for synthesizing functional redox-active materials.Solvent exchange of the frameworks leads to slight modulation of the conductive properties,demonstrating their potential as tunable components in molecula electronic devices.3.Based on the TTF compound containing 3,5-di-tert-butylbenzylthio groups,a novel soluble D-?-A type phthalocyanine compound with four(3,5-di-tert-butylbenzylthio-TTF)structural units 2,3,9,10,16,17,23,24-tetrakis[4',5'-bis(3,5-di-tert-butylbenzylthio)tetrathiafulvale ne]phthalocyanine(9)was synthesized.The structures of its precursor5,6-Didicyano-2-(4,5-bis(3,5-di-tert-butylbenzylthio)-1,3-dithio-2-ylidene)benzo[d]-1,3-dithiole(8)has been determined by X-ray crystallography.In crystal state of compound 8,the TTF portion with phthalonitrile on the same side is almost flat,while the TTF portion with 3,5-di-tert-butylbenzylthio groups is slightly curved.The molecules form the one-dimensional chain structure through nonclassical hydrogen-bond,and the conjugated molecules pack with each other through weak S···S and p···p interactions,while the 3,5-ditert-butylphenyl groups stacking with each other through alkyl.The influence of the electron donating ability of tert-butyl substituents on the characteristic wavelength of phthalocyanine was investigated through UV-vis absorption spectra,and the electrochemical properties showed that the electron donating groups could promote the oxidation of the compounds.The results show that the electron transition and electrochemical activity can be increased by introducing multiple tert-butyl groups.