Organoimido-Polyoxometalate Nonlinear Optical Chromophores: A Structural, Spectroscopic, and Computational Study

Ahmed Al-Yasari, Nick van Steerteghem, Hayleigh Kearns, Hani El Moll, Karen Faulds, Joseph A. Wright, Bruce S. Brunschwig, Koen Clays, John Fielden

Research output: Contribution to journalArticlepeer-review

16 Citations (Scopus)
18 Downloads (Pure)

Abstract

Ten organoimido polyoxometalate (POM) based chromophores have been synthesized and studied by hyperRayleigh Scattering (HRS), Stark and Resonance Raman spectroscopies and DFT calculations. HRS β0 values for chromophores
with resonance electron donors are significant (up to 139 × 10-30 esu, ca. 5 × that of the DAS+ cation), but systems with no donor, or the –NO2 acceptor show no activity, in some cases despite large DFT-predicted β-values. In active systems with short (phenyl) π-bridges, β0-values comfortably exceed that of the purely organic structural analogue N,N-dimethyl-4-nitroaniline (DMPNA), and
intrinsic β-values, β0/N3/2 (N = number of bridge π-electrons) thus appear to break empirical performance limits (β0/N3/2 vs λmax) for planar organic systems. However, β0-values obtained for extended systems with a diphenylacetylene bridge are comparable to or lower than that of their nitro analogue N,N-dimethyl-4-[(4-nitrophenyl)ethynyl]-aniline (DMNPEA). Resonance Raman spectroscopy confirms involvement of the POM in the electronic transitions whether donor groups are present or not, but Stark spectroscopy
indicates that in their absence the transitions have little dipolar character (hence NLO inactive), consistent with DFT-calculated frontier orbitals which extend over both POM and organic group. Stark and DFT also suggest that β is enhanced in the short compounds because extension of charge transfer (CT) onto the POM increases excited state dipole moment changes. With extended π-systems this effect does not increase CT distances relative to a –NO2 acceptor, so β0-values do not exceed that of DMNPEA. Overall, our results show that: (i) the organoimido–POM unit is an efficient acceptor for 2nd order NLO, but an ineffective donor; (ii) the nature of electronic transitions in arylimido-POMs is strongly influenced by the substituents of the aryl group; and (iii) organoimido-POMs outperform organic acceptors with short π-bridges, but lose their advantage with extended π-conjugation.
Original languageEnglish
Pages (from-to)10181–10194
Number of pages14
JournalInorganic Chemistry
Volume56
Issue number17
Early online date15 Aug 2017
DOIs
Publication statusPublished - 5 Sep 2017

Cite this