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Synthesis, crystal structures, linear and nonlinear optical properties, and theoretical studies of (p-R-phenyl)-, (p-R-phenylethynyl)-, and (E)-[2-(p-R-phenyl)ethenyl]dimesitylboranes and related compounds

Yuan, Z.; Entwistle, C.D.; Collings, J.C.; Albesa-Jove, D.; Batsanov, A.S.; Howard, J.A.K.; Taylor, N.J.; Kaiser, H.M.; Kaufmann, D.E.; Poon, S.Y.; Wong, W.Y.; Jardin, C.; Fathallah, S.; Boucekkine, A.; Halet, J.F.; Marder, T.B.

Authors

Z. Yuan

C.D. Entwistle

J.C. Collings

D. Albesa-Jove

J.A.K. Howard

N.J. Taylor

H.M. Kaiser

D.E. Kaufmann

S.Y. Poon

W.Y. Wong

C. Jardin

S. Fathallah

A. Boucekkine

J.F. Halet

T.B. Marder



Abstract

The (p-R-phenyl)dimesitylboranes (R=Me2N, MeO, MeS, Br, I), (p-R-phenylethynyl)dimesitylboranes (R=Me2N, MeO, MeS, H), (E)-[2-(p-R-phenyl)ethenyl]dimesitylboranes (R=Me2N, H2N, MeO, MeS, H, CN, NO2), (E)-[2-(2-thienyl)ethenyl]dimesitylborane, and (E)-[2-(o-carboranyl)ethenyl]dimesitylborane have been prepared through the reaction of the appropriate p-R-phenyl- and p-R-phenylethynyllithium reagents with dimesitylboron fluoride and by hydroboration of the appropriate p-R-phenylacetylene, 2-ethynylthiophene, and o-ethynylcarborane with dimesitylborane. Their UV/Vis absorption and emission spectra have been recorded in a range of solvents with the fluorescence maxima of the donor-substituted compounds in particular exhibiting large bathochromic shifts in highly polar solvents, indicative of charge transfer leading to large dipole moments in the excited state. The molecular structures of the (p-R-phenyl)dimesitylboranes (R=Me2N, MeO, MeS, Br, I), the (E)-[2-(p-R-phenyl)ethenyl]dimesitylboranes (R=Me2N, H2N MeO, MeS, H), (p-R-phenylethynyl)dimesitylborane (R=Me2N), and (E)-[2-(2-thienyl)ethenyl]dimesitylborane, which have been determined from single-crystal X-ray diffraction measurements, offer evidence of increased conjugation in the ground state with increased donor strength of the R substituent. Their first- and second-order molecular hyperpolarizabilities have been obtained from EFISH and THG measurements, the first-order hyperpolarizabilities being largest for the strongest R-substituent donors. AM1 calculations have been performed on these compounds, showing reasonable agreement with the experimentally obtained bond lengths and hyperpolarizabilities, as well as on several related hypothetical compounds containing multiple CC bonds, most of which are proposed to have even larger hyperpolarizabilities.

Citation

Yuan, Z., Entwistle, C., Collings, J., Albesa-Jove, D., Batsanov, A., Howard, J., …Marder, T. (2006). Synthesis, crystal structures, linear and nonlinear optical properties, and theoretical studies of (p-R-phenyl)-, (p-R-phenylethynyl)-, and (E)-[2-(p-R-phenyl)ethenyl]dimesitylboranes and related compounds. Chemistry - A European Journal, 12(10), 2758-2771. https://doi.org/10.1002/chem.200501096

Journal Article Type Article
Publication Date Mar 20, 2006
Deposit Date Apr 20, 2007
Journal Chemistry - A European Journal
Print ISSN 0947-6539
Electronic ISSN 1521-3765
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 12
Issue 10
Pages 2758-2771
DOI https://doi.org/10.1002/chem.200501096
Keywords Boranes, Nonlinear optics, Semiempirical calculations, Synthetic methods, X-ray diffraction.