Synthesis and Properties of two CuI Complexes Involving Tetrathia-fulvalene-Fused Phenanthroline Ligand.

Zhi-Gang Niu,Sun Wei,Guang-Ying Chen,Xue-You Wang,Hao-Hua Chen,Dong-Min Wu,Jie Qin,Xun Wang,Gao-Nan Li

doi:10.17344/acsi.2017.3423

Abstract

Two CuI complexes based on the π-conjugated tetrathiafulvalene-annulated phenanthroline ligands (TTF-Phen, L1 and L2), [CuI(Xantphos)(L1)]BF4 (1, Xantphos = 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene) and [CuI(Binap)(L2)]BF4 (2, Binap = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl), have been synthesized. They have been fully characterized, and their photophysical and electrochemical properties are reported together with those of L1 and L2 for comparison. Both CuI complexes show metal-to-ligand charge transfer (MLCT) absorption bands, whereas the 3MLCT luminescence is strongly quenched.

Highlights

An established strategy for the preparation of such molecular materials is the combination of functional groups and electro-active TTF moieties.[4,5,6,7]
In the past years this strategy has led to materials exhibiting novel photofunctional properties, such as fluorescence switches, metal ion sensors, photovoltaic cells, and nonlinear optics.[8,9,10,11]
We recently reported two TTF-based CuI complexes, [CuI(Binap)(TTF-TzPy)]BF4 and [CuI(Xantphos)(TTF-TzPy)]BF4, which exhibit interesting electrochemical and photophysical properties.[13]

Summary

Introduction

In the recent study of TTF chemistry, multifunctional molecular material involving interplay and synergy between multiple physical properties have received considerable attention.[1,2,3] An established strategy for the preparation of such molecular materials is the combination of functional groups and electro-active TTF moieties.[4,5,6,7] in the past years this strategy has led to materials exhibiting novel photofunctional properties, such as fluorescence switches, metal ion sensors, photovoltaic cells, and nonlinear optics.[8,9,10,11] Following this strategy, we recently reported two TTF-based CuI complexes, [CuI(Binap)(TTF-TzPy)]BF4 and [CuI(Xantphos)(TTF-TzPy)]BF4, which exhibit interesting electrochemical and photophysical properties.[13]. In this paper, we use more π-conjugated TTF-Phen ligand instead of TTFTzPy ligand to form two CuI complexes, [CuI(Xantphos)(L1)]BF4 (1, Xantphos = 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene) and [CuI(Binap)(L2)]BF4 (2, Binap = 2,2’-bis(diphenylphosphino)-1,1’-binaphthyl). The photophysical and electrochemical properties of these complexes are investigated

Experimental

Results and Discussion

Conclusions