Coumarinyl azoimidazolyl complexes of osmium(II) hydridocarbonyls: spectroscopic and structural characterization, oxidation catalysis, photovoltaic effect and density functional theory computation

Abstract

Os(II) hydridocarbonyl complexes of coumarinyl azoimidazoles, [Osh(CO)(PPh3)2(CZ‐4R‐R′)]0/+ (3, 4) (CZ‐R‐H = 2‐(coumarinyl‐6‐azo)‐4‐substituted imidazole or 1‐alkyl‐2‐(coumarinyl‐6‐azo)‐4‐substituted imidazole), were characterized from spectroscopic data and the single‐crystal X‐ray data for one of the complexes, [Osh(CO)(PPh3)2(CZ‐4‐Ph)] (3c) (CZ‐4‐Ph = 2‐(coumarinyl‐6‐azo)‐4‐phenylimidazolate), confirmed the structure. The complexes show higher emission (quantum yield ϕ = 0.0163–0.16) and longer lifetime (τ = 1.4–10.3 ns) than free ligands (ϕ = 0.0012–0.0185 and τ = 0.685–1.306 ns). Cyclic voltammetry shows quasi‐reversible metal oxidation at 0.67–0.94 V for [Os(III)/Os(II)] and 1.21–1.36 V for [Os(IV)/Os(III)] and subsequent azo reductions (−0.68 to −0.95 V for [NN]/[N N]− and irreversible < −1.2 V for [N N]−/[NN]2−) of the chelated coumarinyl azoimidazole. The complexes are photostable and show better photovoltaic power conversion efficiency than free ligands. Also, the complexes were used as catalysts for the oxidation of primary/secondary alcohols to aldehydes/ketones using oxidizing agents like N‐methylmorpholine N‐oxide, t‐BuOOH and H2O2. Density functional theory computation was carried out from the optimized structures and the data obtained were used to interpret the electronic and photovoltaic properties. Copyright © 2016 John Wiley & Sons, Ltd.