Issue 18, 2023

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 E1/2 = −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 Image ID:d3dt00351e-t1.gif 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 Image ID:d3dt00351e-t2.gif values, both complexes were evaluated as potential photosensitisers for halogen atom transfer (XAT) using a test reaction of the dehalogenation of benzyl chloride.

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

Supplementary files

Article information

Article type
Paper
Submitted
03 Yan 2023
Accepted
04 Dzi 2023
First published
05 Dzi 2023

Dalton Trans., 2023,52, 5909-5917

Author version available

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

P. Pandey, Q. Yang, M. R. Gau and E. J. Schelter, Dalton Trans., 2023, 52, 5909 DOI: 10.1039/D3DT00351E

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