Donor and geometry optimization: Fresh perspectives for the design of polyoxometalate charge transfer chromophores

Hood, Bethany R., de Coene, Yovan, Jones, Claire F., Deveaux, Noah, Barber, Jack M., Marshall, Charlotte G., Jordan, Chloe A., Halcovitch, Nathan R., Champagne, Benoît, Clays, Koen and Fielden, John (2025) Donor and geometry optimization: Fresh perspectives for the design of polyoxometalate charge transfer chromophores. Inorganic Chemistry, 64 (16). pp. 8408-8420. ISSN 0020-1669

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Abstract

Three linear, dipolar arylimido-polyoxometalate (POM) and one 2-dimensional bis-functionalized arylimido-polyoxometalate charge transfer chromophore, with diphenylacetylene bridges, have been synthesized and studied by spectroelectrochemistry, hyper-Rayleigh scattering (HRS), and DFT/TD-DFT calculations. The linear systems show that with julolidinyl (Jd) and −NTol2 donor groups, the alkyne bridge yields high second-order nonlinear optical (NLO) coefficients β (Jd, β0,zzz = 318 × 10–30 esu; −NTol2, β0,zzz = 222 × 10–30 esu), indeed the Jd compound gives the highest NLO activity of any organoimido-POM to date with minimal decrease in transparency. The bis-functionalized 2D (C2v) POM derivative showed increased activity over its monofunctionalized analogue with no decrease in transparency, although the NLO response was only minimally two dimensional. Spectroelectrochemistry and TD-DFT calculations showed switchable linear optical responses for the monofunctionalized derivatives due to the weakened charge transfer character of the electronic transitions in the reduced state, while TD-DFT also indicated potential for switched NLO responses. These have been demonstrated by electrochemistry-HRS for the Jd compound, but cyclability is limited by relatively poor stability in the reduced state. IR and CV studies for these sterically protected arylimido polyoxometalates indicate that decomposition proceeds via a breakdown of the {Mo6} cluster in the reduced state, rather than simple solvolysis of the Mo≡N bond.

Item Type:	Article
Additional Information:	Acknowledgments: We thank the EPSRC for support through grant EP/M00452X/1 to J.F.. X-ray data were obtained in facilities established by EPSRC grant EP/S005854/1. B.R.H. thanks the University of East Anglia for a studentship and Lancaster University for short-term postdoctoral support. C.F.J. and J.F. acknowledge funding from the Leverhulme Trust (RPG-2020-365). Y.D.C. acknowledges the Fonds Wetenschappelijk Onderzoek (FWO) for senior postdoc (No. 1268825N). N.D. thanks the F.R.S-FNRS and the Walloon Region for his FRIA grant. Calculations were performed on the Consortium des Équipements de Calcul Intensif (CECI, http://www.ceci-hpc.be) 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 (Convention Nos. GEQ U.G006.15, U.G018.19, U.G011.22, RW1610468, RW/GEQ2016, RW1117545, and RW2110213).
Faculty \ School:	Faculty of Science > School of Chemistry (former - to 2024) Faculty of Science > School of Chemistry, Pharmacy and Pharmacology
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
Depositing User:	LivePure Connector
Date Deposited:	09 May 2025 16:30
Last Modified:	09 May 2025 19:30
URI:	https://ueaeprints.uea.ac.uk/id/eprint/99236
DOI:	10.1021/acs.inorgchem.5c00915

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