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

Al-Yasari, Ahmed, El Moll, Hani, Purdy, Ryan, Vincent, Kevin B., Spence, Philip, Malval, Jean-Pierre and Fielden, John (2021) Optical, third order non-linear optical and electrochemical properties of dipolar, centrosymmetric and C2v organoimido polyoxometalate derivatives. Physical Chemistry Chemical Physics, 23 (20). pp. 11807-11817. ISSN 1463-9076

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Abstract

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.

Item Type: Article
Uncontrolled Keywords: physics and astronomy(all),physical and theoretical chemistry ,/dk/atira/pure/subjectarea/asjc/3100
Faculty \ School: Faculty of Science > School of Chemistry
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Depositing User: LivePure Connector
Date Deposited: 08 May 2021 00:04
Last Modified: 21 Sep 2021 01:30
URI: https://ueaeprints.uea.ac.uk/id/eprint/79956
DOI: 10.1039/D0CP06610A

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