Optical, third order non-linear optical and electrochemical properties of dipolar, centrosymmetric and C2v organoimido polyoxometalate derivatives

Ahmed Al-Yasari, Hani El Moll, Ryan Purdy, Kevin B. Vincent, Philip Spence, Jean-Pierre Malval, John Fielden

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A family comprising seven arylimido-polyoxometalate (POM) hybrid chromophores (three of which are new), with linear dipolar,C 2vand linear centrosymmetric geometries have been synthesised and studied by electronic absorption spectroscopy, electrochemistry, Z-scans (two photon absorption, TPA) and computation (DFT/TD-DFT). These reveal that POM acceptor units are an effective basis for TPA materials: the centrosymmetric bis-POM chromophores produce significant cross sections (δup to 82 GM) from a single aryl bridge, a similar performance to larger dipolar π-systems combining carbazole or diphenylamino donors with the imido-POM acceptor. DFT/TD-DFT calculations indicate strong communication between POM and organic components is responsible for the linear and non-linear optical behaviour of these compounds, while electrochemical measurements reveal class II mixed valence behaviour resulting from an interplay of through-bond and through-space effects.

Original languageEnglish
Pages (from-to)11807-11817
Number of pages11
JournalPhysical Chemistry Chemical Physics
Issue number20
Early online date7 May 2021
Publication statusPublished - 28 May 2021

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