Fine-tuning polyoxometalate non-linear optical chromophores: a molecular electronic "Goldilocks" effect

Ahmed Al-Yasari; Philip Spence; Hani El Moll; Nick Van Steerteghem; Peter N Horton; Bruce S Brunschwig; Koen Clays; John Fielden

doi:10.1039/c8dt01491d

Fine-tuning polyoxometalate non-linear optical chromophores: a molecular electronic "Goldilocks" effect

Dalton Trans. 2018 Aug 21;47(31):10415-10419. doi: 10.1039/c8dt01491d. Epub 2018 Jun 27.

Authors

Ahmed Al-Yasari¹, Philip Spence², Hani El Moll², Nick Van Steerteghem³, Peter N Horton⁴, Bruce S Brunschwig⁵, Koen Clays³, John Fielden²

Affiliations

¹ School of Chemistry, University of East Anglia, Norwich, NR4 7TJ, UK. John.Fielden@uea.ac.uk and College of Pharmacy, University of Kerbala, Kerbala, Iraq.
² School of Chemistry, University of East Anglia, Norwich, NR4 7TJ, UK. John.Fielden@uea.ac.uk.
³ Department of Chemistry, University of Leuven, Celestijnenlaan 200D, B-3001 Leuven, Belgium.
⁴ UK National Crystallography Service, School of Chemistry, University of Southampton, Southampton, SO17 1BJ, UK.
⁵ Beckman Institute, MC 139-74, California Institute of Technology, 1200 East California Blvd, Pasadena, CA 91125, USA.

PMID: 29947391
DOI: 10.1039/c8dt01491d

Abstract

A new aryl-imido polyoxometalate non-linear optical chromophore (POMophore) with a diphenylamino donor group attains the highest β_{zzz, 0} value (196 × 10^-30 esu by Hyper-Rayleigh Scattering, HRS), and best transparency/non-linearity trade off yet for such materials. Stark spectroscopic and DFT investigation of this compound, plus NMe₂ and carbazole analogues, show that its high performance results from a combination of strongly dipolar electronic transitions, and strong electronic communication across the π-system.