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

A family comprising seven arylimido-polyoxometalate (POM) hybrid chromophores (three of which are new), with linear dipolar, C2v and linear centrosymmetric geometries have been synthesised and studied by electronic absorption spectroscopy, electrochemistry, Z-scans (two photon absorption, TPA) and c...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2021-05, Vol.23 (20), p.11807-11817
Main Authors: Al-Yasari, Ahmed, Hani El Moll, Purdy, Ryan, Vincent, Kevin B, Spence, Philip, Malval, Jean-Pierre, Fielden, John
Format: Article
Language:English
Subjects:
Carbazoles
Chromophores
Crystallography
Donors (electronic)
Electrochemical analysis
Electrochemistry
Optical properties
Photon absorption
Polyoxometallates
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Summary:A family comprising seven arylimido-polyoxometalate (POM) hybrid chromophores (three of which are new), with linear dipolar, C2v and 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 (δ up 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.
ISSN:1463-9076
1463-9084
DOI:10.1039/d0cp06610a