Studies On TTF-copper Polymers And Mebpe-metal Halides With Redox Function

Tetrathiafulvalene?TTF?,a sulfur-rich system,can be reversibly oxidized to the corresponding radical cation(TTF^·+)and is a very good conductor.Attempts have been made to introduce functional groups into the TTF system and combine TTF with metals in order to obtain photovoltaic materials.In addition,the pyridine group has a strong ability to coordinate metal and can be transformed to a positively charged pyridinium salt.1,2-di?4-pyridyl?ethylene?bpe?has similarity to TTF because of its conjugated structure and excellent redox properties,which has attracted great attention.Although metal coordination polymers of carboxylic acid-based TTFs have been reported,the construction of three-dimensional coordination frameworks for TTF pyridine derivatives,especially bipyridine derivatives,is extremely limited.One of the tasks of this project is to integrate TTF-pyridine derivative with metal ions to construct three-dimensional?3D?framework and to investigate the redox and photoelectric properties.Due to the rising interests of organic-inorganic hybrid perovskite,the second task of this project is to combine methylated bpe?Mebpe?with lead and bismuth halides to synthesize perovskite-like compounds.Charge transfer,redox and photoelectric properties have been studied.This work has a certain significance in the development of new photoelectric materials.The major contents are as follows:1?Introduction,the properties and research progress of TTF and bpe derivatives are reviewed briefly.Recent researches on TTF derivatives substituted by pyridine are summarized.Finally,the significance and the main contents of the thesis are introduced.2?A 3D copper-tetrathiafulvalene compound{[Cu?py-TTF-py?₂]ClO₄·H₂O}_n is obtained.C rystal structure analysis shows that the compound possesses highly unusual8-fold interpenetration diamond-like structure.UV-visible spectrum reveals that the charge-transfer occurred after the formation of the complex.Cyclic voltammetry?CV?shows that the compound is redox-active.The photocurrent test was carried out and the results show that the photocurrent intensity is related to the redox state of the network.3?Redox-active bi-methylated 1,2-di?4-pyridyl?ethylene?Mebpe?was introduced into metal halides to obtain three compounds{?Mebpe?₂[Pb₃I₁₀]}_n?2?,{?Mebpe?[?PbI₃?₂]}_n?3?,[?Mebpe?₂·(Bi₄I₁₆)]·2CH₃OH?4?.X-ray single crystal analyses show that halide anions have a one-dimensional chain structure in compounds 2 and 3,and a 4-core structure in compound 4.UV-visible spectra reveal that the charge-transfer occurred after the formation of compounds.CV curves show the redox properties of compounds 2-4,which means that they are excellent redox materials.The photocurrent tests confirm the better responses of compounds compared with Mebpe.4?In summary,this section contains the conclusion of this paper.O utlook is made for the future work.