화학공학소재연구정보센터
Inorganic Chemistry, Vol.59, No.5, 2781-2790, 2020
Trifluoromethylated Phenanthroline Ligands Reduce Excited-State Distortion in Homoleptic Copper(I) Complexes
We report the synthesis and excited-state dynamics for a series of homoleptic copper(I) trifluoromethylated phenanthroline complexes with two, three, and four trifluoromethyl functional groups. Our analysis of the steady-state absorbance and emission, transient-absorption spectroscopy, and electronic-structure-theory calculations results enable in-depth analysis of the pseudo-Jahn-Teller distortion inhibition from increased steric hindrance of the trifluoromethyl functional group relative to the prototypical dimethyl phenanthroline complex. Surprisingly, our results demonstrate that the greatest degree of pseudo-Jahn-Teller distortion inhibition is achieved with trifluoromethylation of only the 2 and 9 positions by an unusual combination of steric hindrance and stabilization of a nondistorted (MLCT)-M-1 manifold observed by transient kinetic lifetimes and optimized excited-state structures. The intersystem-crossing (ISC) lifetime for the 2,9-bis(trifluoromethyl)-1,10-phenanthroline Cu(I) complex is 69 ps, while the triplet excited-state lifetime and emission quantum yield are 106 ns and 4 x 10(-3), respectively. Further trifluoromethylation of the phenanthroline yields a greater t bond inductive withdrawing force on the phenanthroline nitrogens, ultimately resulting in weaker coordination to the copper. Last, the surprising success of the 2,9-bis(trifluoromethyl)-1,10-phenanthroline Cu(I) complex by adjusting both ligand sterics and electronic properties outlines a new strategy for developing long-lived Cu(I) charge-transfer complexes.