Synthesis And Properties Of Ferrocene Compounds With D-π-A Structure

Ferrocene has advantages such as unique rigid and rich electronic structure, reversibility oxidation-reduction ability, and easily being modification. Ethynylferrocene, which combines the advantage of ferrocene group and acetylene groups, will be a rigid construction unit to build novel molecular structure with photoelectric activities. This thesis has designed and synthesized three types of 12 kinds of conjugated ethynylferrocene derivatives, which could be applied to dye sensitized solar cells (DSSCs) and anion recognition.Four conjugated ethynylferrocene derivatives with aldehyde group (Fc-X-Aldehyde), which were 4-ferrocene ethynyl benzaldehyde (Fc-Ph-Aldehyde),5-ferrocene ethynyl thiophene-1-aldehyde (Fc-Thie-Aldehyde), N-ethyl-6-ferrocene ethynyl carbazole-3-aldehyde (Fc-Cz-Aldehyde), N-ethyl-6-ferrocene ethynyl phenothiazine-3-aldehyde (Fc-PTZ-Aldehyde) respectively, were synthesized via Sonogashira coupling reaction of ethynyl ferrocene with 4-bromobenzaldehyde,2-bromo-5-formylthiophene, 3-bromo-9-ethylcarbazole-6-carboxaldehyde 7-bromo-10-ethy1-10H-phenothiazine-3-carboxaldehyde respectively.Four D-π-A conjugated ethynylferrocene dyes containing carboxyl group (Fc-X-C) were prepared by Knoevenagel condensation reaction of Fc-X-Aldehyde and cyano acetic acid. They were 3-(4-(ferrocenylethynyl)phenyl)-2-cyano-acrylic acid (Fc-Ph-C),3-(5-(ferro cenylethynyl)thienyl)-2-cyano-acrylic acid (Fc-Thie-C),3-((6-ferrocenyl ethynyl)-9-ethyl-9H-carbazol-3-yl)-2-cyano-acrylic acid (Fc-Cz-C) and 3-((7-ferrocenyl-ethynyl)-10-ethyl-10H-phenothiazin-3-yl)-2-cyano-acrylic acid (Fc-PTZ-C) respectively.Four ethynylferrocene based semicarbazide derivatives (Fc-X-An) were prepared through the reaction of Fc-X-Aldehyde with semicarbazide hydrochloride, which were 2-(4-(ferrocenylethynyl)benzylidene) hydrazine-1-carboxamide (Fc-Ph-An),2-((5-(ferrocenylethynyl) thiophen-2-yl )methylene)hydrazine-1-carboxamide (Fc-Thie-An),2-((9-ethyl-6-(ferrocenyl-ethynyl)-9H-carbazol-3-yl) methylene)hydrazine-1-carboxamide (Fc-Cz-An) and 2-((10-ethyl-7-(ferrocenylethynyl)-1 OH-phenothiazin-3-y l)methylene) hydrazine-1-carboxamide (Fc-PTZ-An).All products were characterized by IR,1H NMR and 13C NMR. Their structures were optimized through the quantum chemistry calculation and molecular frontier orbital analysis. The physical properties were studied via UV-vis absorption spectroscopy, fluorescence spectroscopy and cyclic voltammetry.The J-V curves were studied to test the performance of Fc-X-C used as sensitizers in DSSCs. The results showed that cobalt electrolyte had higher efficiency than that of iodine electrolyte and Fc-PTZ-C obtained the best photoelectric conversion rate as high as 1.06%. Four kinds of Fc-X-An molecules for selective anion recognition were researched, the results showed that they all had significant selective recognition of F". The coordination constants, detection of limit and the coordination ratio were got through Benesi-Hildebrand equation and Job plot. Besides fluorescence titration spectroscopy, titration of cyclic voltammetry and nuclear magnetic titration of Fc-X-An in DMSO-d6 solution have also been studied for identification the recognition process between Fc-X-An and F-.