Bridge improvement work: maximising non-linear optical performance in polyoxometalate derivatives

Jones, Claire F. and Hood, Bethany R. and de Coene, Yovan and Lopez-Poves, Ivan and Champagne, Benoît and Clays, Koen and Fielden, John (2024) Bridge improvement work: maximising non-linear optical performance in polyoxometalate derivatives. Chemical Communications, 60 (13). pp. 1731-1734. ISSN 1359-7345

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Abstract

New phenyl and stilbene-bridged polyoxometalate (POM) charge-transfer chromophores with diphenylamino donor groups produce, respectively, the highest intrinsic and absolute quadratic hyperpolarisabilities measured for such species. The β 0,zzz obtained for the phenyl bridge - at 180 × 10 −30 esu - is remarkable for a short conjugated system while changing to the stilbene (260 × 10 −30 esu) produces a substantial increase in non-linearity for a minimal red-shift in the absorption profile. Together with TD-DFT calculations, the results show that maximising conjugation in the π-bridge is vital to high performance in such “POMophores”.