Remarkable NLO response and infrared absorption in simple twisted molecular π-chromophores

I. D L Albert, Tobin J Marks, M. A. Rather

Research output: Contribution to journalArticle

136 Citations (Scopus)

Abstract

Computational modeling reveals that, by substitutional modification of interplanar dihedral angles in a series of quinopyrans, both the optical absorption cross section and the first hyperpolarizability can be widely tuned in both frequency and magnitude. This is a promising structural control scheme for modulating molecular nonlinear optical and infrared absorption properties. The maximum nonresonant μβ estimated for a tetraalkyl- substituted 4-quinopyran, the full AM1-optimized interplanar dihedral angle of which is 104°, is ~70000 x 10-48 esu, at an excitation energy of 0.10 eV. This is 4 orders of magnitude larger than that of the archetypical NLO chromophore, 4-N,N'-(dimethylamino)-4'-nitrostilbene, at the same excitation frequency. The effects of conjugation pathway, strength of the electron donor/acceptor groups, and auxiliary donor and acceptor on the molecular response properties have also been analyzed. The optical absorption at a twist angle of 90% when the molecule can be described as two disjoint π- subfragments, exhibits characteristic absorptions from the individual subfragments and also inter-subfragment excitation; the former occur at high energies and with high oscillator strengths, while the latter occurs at low energy and with low oscillator strength.

Original languageEnglish
Pages (from-to)11174-11181
Number of pages8
JournalJournal of the American Chemical Society
Volume120
Issue number43
DOIs
Publication statusPublished - Nov 4 1998

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Infrared absorption
Chromophores
Light absorption
Dihedral angle
Excitation energy
Molecules
Electrons

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Remarkable NLO response and infrared absorption in simple twisted molecular π-chromophores. / Albert, I. D L; Marks, Tobin J; Rather, M. A.

In: Journal of the American Chemical Society, Vol. 120, No. 43, 04.11.1998, p. 11174-11181.

Research output: Contribution to journalArticle

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