Evaluating the photophysical and photochemical characteristics of green-emitting cerium(iii) mono-cyclooctatetraenide complexes

Abstract

The photophysical and photochemical reactivity of the organometallic mono(cyclooctatetraenide)-Ce(III) complexes: [(C₈H₈)Ce(μ-X)(THF)₂]₂ X = O₃SCF₃⁻ (1), Cl⁻ (2), were studied. In the course of these studies, a new polymorph of [(C₈H₈)Ce(μ-O₃SCF₃)(THF)₂]₂ (1) was described. Photoluminescence (PL) studies of 1 and 2 showed characteristic excitation and emission bands in the visible region, with bright green light emission under light irradiation from states corresponding to the 5d → 4f transition. Complexes 1 and 2 exhibit relatively long lifetime of 205.4 ± 0.2 and 145.8 ± 0.4 ns respectively. And the quantum yields (Φ) for 1 and 2 are 0.180 and 0.068 respectively. Electrochemical studies were performed on complexes 1 and 2 with a reversible Ce(III)/Ce(IV) redox couple recorded at E_1/2 = −1.53 V versus the Fc/Fc⁺ for 2. Complex 1 shows an irreversible Ce(III/IV) oxidation wave. Complexes 1 and 2 revealed strongly-reducing, estimated, excited state reduction potentials of −3.31 and −4.02 V versus the Fc/Fc⁺ respectively, with small Stokes shifts of 0.12 eV. With their associated relatively long lifetimes, small Stokes shifts and large, negative values, both complexes were evaluated as potential photosensitisers for halogen atom transfer (XAT) using a test reaction of the dehalogenation of benzyl chloride.