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

Jones, Claire F., Hood, Bethany R., de Coene, Yovan, Lopez-Poves, Ivan, Champagne, Benoît, Clays, Koen and Fielden, John ORCID: (2024) Bridge improvement work: Maximising non-linear optical performance in polyoxometalate derivatives. Chemical Communications, 60 (13). pp. 1731-1734. ISSN 1359-7345

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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 β0,zzz obtained for 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”.

Item Type: Article
Additional Information: Funding information: The authors thank the EPSRC for support through grant EP/M00452X/1 to JF, X-ray data were obtained in facilities established by EPSRC grant EP/S005854/1. BRH thanks the University of East Anglia for a studentship and Lancaster University for short-term postdoctoral support. CFJ and JF acknowledge funding from the Leverhulme Trust (RPG-2020-365) and thank Dr Joseph Wright of the University of East Anglia for assistance in re-synthesis of 3. YDC acknowledges the Fonds Wetenschappelijk Onderzoek (FWO) for junior postdoc (No 1234222N). Calculations were performed on the UEA High Performance Cluster, Consortium des Equipements de Calcul Intensif (CECI, and the Technological Platform of High-Performance Computing, for which the authors acknowledge the financial support of the FNRS-FRFC, the Walloon Region, and University of Namur (Conventions No. 2.5020.11, GEQ U.G006.15, U.G018.19, U.G011.22, 1610468, and RW/GEQ2016). Data availability: In addition to the ESI and deposited cif files, data can be obtained by contacting the corresponding author.
Faculty \ School: Faculty of Science > School of Chemistry
UEA Research Groups: Faculty of Science > Research Groups > Energy Materials Laboratory
Faculty of Science > Research Groups > Chemistry of Materials and Catalysis
Faculty of Science > Research Groups > Chemistry of Light and Energy
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Depositing User: LivePure Connector
Date Deposited: 18 Jan 2024 01:36
Last Modified: 03 Jun 2024 13:31
DOI: 10.1039/D3CC05433K


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