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

Published on 2017-09-14T04:30:26Z (GMT) by
Ten organoimido polyoxometalate (POM)-based chromophores have been synthesized and studied by hyper-Rayleigh scattering (HRS), Stark and Resonance Raman spectroscopies, and density functional theory (DFT) calculations. HRS β<sub>0</sub> values for chromophores with resonance electron donors are significant (up to 139 × 10<sup>–30</sup> esu, ∼5 times greater than that of the DAS<sup>+</sup> cation), but systems with no donor, or the −NO<sub>2</sub> acceptor show no activity, in some cases, despite large DFT-predicted β-values. In active systems with short (phenyl) π-bridges, β<sub>0</sub> values comfortably exceed that of the purely organic structural analogue <i>N</i>,<i>N</i>-dimethyl-4-nitroaniline (DMPNA), and intrinsic β-values, β<sub>0</sub>/N<sup>3/2</sup> (where <i>N</i> is the number of bridge π-electrons) thus appear to break empirical performance limits (β<sub>0</sub>/N<sup>3/2</sup> vs λ<sub>max</sub>) for planar organic systems. However, β<sub>0</sub> values obtained for extended systems with a diphenylacetylene bridge are comparable to or lower than that of their nitro analogue, <i>N</i>,<i>N</i>-dimethyl-4-[(4-nitrophenyl)­ethynyl]-aniline (DMNPEA). Resonance Raman spectroscopy confirms the 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 the extension of charge transfer (CT) onto the POM increases changes in the excited-state dipole moment. With extended π-systems, this effect does not increase CT distances, relative to a −NO<sub>2</sub> acceptor, so β<sub>0</sub> values do not exceed that of DMNPEA. Overall, our results show that (i) the organoimido–POM unit is an efficient acceptor for second-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.

Cite this collection

Al-Yasari, Ahmed; Steerteghem, Nick Van; Kearns, Hayleigh; Moll, Hani El; Faulds, Karen; Wright, Joseph A.; Brunschwig, Bruce S.; Clays, Koen; Fielden, John (2017): Organoimido-Polyoxometalate Nonlinear Optical Chromophores:

A Structural, Spectroscopic, and Computational Study. ACS Publications.

https://doi.org/10.1021/acs.inorgchem.7b00708

Retrieved: 05:28, Sep 20, 2017 (GMT)