Exploration of the remarkable second-order nonlinear optical response of new POM-cyclometalated platinum complexes

New inorganic-organometallic hybrid hexamolybdate-cyclometalated platinum materials were computationally designed and investigated, via both density functional theory (DFT) and time-dependent density functional theory (TD-DFT), as second-order nonlinear chromophores. The geometric and electronic structures, linear optical, and second-order nonlinear actives of the systems under study were also evaluated. After connection of cyclometalated platinum complexes to a Lindqvist-type organoimido-hexamolybdate, the resultant chromophores were found to display remarkable second-order nonlinear responses, notably with calculated static first hyperpolarizability, β _0,zzz, responses of up to 224 × 10 ⁻³⁰ esu for anion 1, that is, to date, the most remarkable in terms of performance among POM-based chromophores, with a good trade-off between transparency and nonlinearity being retained compared to similar organic systems.