The Design, Synthesis And Optoelectronic Properties Of Ferrocene-alkynyl Terpyridine Complexes

In recent years, the design, synthesis and properties study of ferrocene-based optoelectronic functional molecules have always been one of the hot research topic of organic functional materials. Ferroceneacetylene has the both advantages of ferrocene and acetylene. So ferroceneacetylene as a rigid building block is widely used in construction of π-conjugated organic functional materials. Due to a unique function of tridentate coordination and good coordination ability with transition metal, terpyridine is widely used in the design and synthesis of π-conjugated organic ligands. In this paper, the combination of the advantages of ferrocene-alkynyl and terpyridyl, a series of ferrocene-containing alkynyl π-conjugated organic molecules and their corresponding ruthenium, platinum complexes were successfully synthesized. The optoelectronic properties of all target molecules were investigated. This article consists of the following three parts:1, The research progresses of ferrocene-alkynyl molecules, ferrocene-based terpyridine ruthenium complexes and alkynyl platinum terpyridine complexes in organic optoelectronic functional molecules were described in this part in detail.2, Alkynyl bridged binuclear ferrocenyl terpyridine functional molecule (13) and three ruthenium complexes (14-16) have been synthesized. All target molecules were investigated by CV, UV-Vis absorption, fluorescence spectrum and quantum chemical simulation optimization. All the ruthenium complexes have luminescence in H2O/CH3CN (4/1) solution at room temperature and the maximum emission wavelength in the vicinity of 736 nm. The MMLCT and MLCT characteristic absorption peaks of the ruthenium complexes were observed in UV-Vis absorption spectrum. Electrochemical research shows that there is a strong electronic interaction proved by the △E1/2 of biferrocene and the push-pull group in 4’-substituted terpyridine have a weak regulation of intramolecular electron interactions.3, Ferrocene-alkynyl platinum terpyridine complexes (27、28、30、31) and phenylacetylene platinum terpyridine complexes (29) have been synthesized. All target molecules were investigated by CV, UV-Vis abosorption and fluorescence spectrum. The electrochemical results indicated that all the complexes exhibit quasi-reversible redox process. In addition, the biferrocene complexes (30,31) have a strong electronic interaction on two ferrocenyl group and its redox property was affected by different counterions. The MLCT characteristic absorption peaks (κmax= 418 nm) of the platinum complexes were observed in UV-Vis abosorption spectrum. All the platinum complexes have luminescence in CH3CN solution at room temperature and the maximum emission wavelength in the vicinity of 289 nm、389 nm. Furthermore, their fluorescence intensity was affected by the counterion ions.