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

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".