Second-order nonlinear optical properties of the four tetranitrotetrapropoxycalix[4]arene conformers

Paul J.A. Kenis, Oscar F.J. Noordman, Stephan Houbrechts, Gerrit J. Van Hummel, Sybolt Harkema, Frank C.J.M. Van Veggel, Koen Clays, Johan F.J. Engbersen, Andre Persoons, Niek F. Van Hulst, David N. Reinhoudt

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This paper reports a systematic experimental and theoretical study of the second-order nonlinear optical properties of multichromophoric molecules that range from dipolar symmetry to three-dimensional octupolar symmetry. The four possible conformers of tetranitrotetrapropoxycalix[4]arene (cone, paco, 1,2-alt, 1,3-alt) were studied by nanosecond hyper-Rayleigh scattering and a newly developed time-resolved femtosecond hyper-Rayleigh scattering technique. The latter enables to correct for long-lived fluorescence contributions to the second harmonic scattering intensity. The depolarization ratios D(x/2) prove the (partial) octupolar symmetry of the 1,2-alt and 1,3- alt conformers, and thus explain why their hyperpolarizabilities β(FHRS) are of the same order of magnitude as those of the dipolar cone and paco conformers. The corresponding theoretical second-order nonlinear optical properties (both β(FHRS) and D(x/2)) were calculated using the conformations obtained from single-crystal X-ray diffraction, molecular mechanics (MM), and molecular dynamics (MD) calculations. In contrast with sum-over-state calculations presented in the literature, our theoretical method takes also into account octupolar contributions by linearly adding the NLO-properties of the separate chromophoric groups and using Bersohn's theory. The agreement between experimental and theoretical results is good both for the conformers having dipolar symmetry and for the conformers having (partly) three- dimensional octupolar symmetry. The 1,2-alt and 1,3-alt conformers of the tetranitrotetrapropoxycalix-[4]arene represent the first examples of multichromophoric molecules that have high hyperpolarizabilities β due to 3D octupolar symmetry.

Original languageEnglish (US)
Pages (from-to)7875-7883
Number of pages9
JournalJournal of the American Chemical Society
Issue number31
StatePublished - Aug 12 1998
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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