ABSTRACT
Cationic [Cu(P^P)(Htbz)]PF6 [P^P = xantphos, dpephos; Htbz = 2-(4-thiazolyl)benzimidazole] and the corresponding neutral complexes [Cu(P^P)(tbz)], obtained through deprotonation of the diimine ligand, have been synthesized with the aim of analyzing the role of the diphosphane and Htbz deprotonation in the emissive properties of these complexes. For the study of the diphosphane effect, the luminescence properties of these compounds have been compared with those of the reported analogous derivatives with Htbz and carborane diphosphanes. Complexes [Cu(P^P)(Htbz)]PF6 (P^P = xantphos, dpephos) and [Cu(dpephos)(tbz)] display thermally activated delayed fluorescence, which has been studied, revealing a ΔE(S1-T1) between 658 and 455 cm-1. Theoretical calculations indicate different origins for the absorptions, leading to the observed emissions.
ABSTRACT
Ortho-closo or ortho-nido-carborane-diphosphanes have been selected to prepare the heteroleptic cationic or neutral [Cu(N^N){(PPh2)2C2B10H10}]PF6 (1) and [Cu(N^N){(PPh2)2C2B9H10}] (2) [N^N = 2-(4-thiazolyl)benzimidazole], respectively. Complexes 1 and 2 display very different emissive behavior. Neutral complex 2 exhibits TADF (time activated delayed fluorescence) which has been studied both as powder and PMMA composite with similar ΔE(S1 - T1), τ(T1), and τ(S1) in both phases. Cationic complex 1 displays a much lower quantum yield than 2 and does not show TADF, but it exhibits a significant thermochromic luminescence, and its emission is very dependent on the medium. Theoretical studies show that metal-ligand (M-diphosphane) to ligand (L', diimine) transitions, MLL'CT, are responsible of the transitions which originate the emissive properties, but with very different contribution of the copper center, carborane cluster, and diphosphane phenyl rings for 1 and 2.
