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

被引:158
作者
Albert, IDL
Marks, TJ
Ratner, MA
机构
[1] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA
[2] Northwestern Univ, Mat Res Ctr, Evanston, IL 60208 USA
关键词
D O I
10.1021/ja982073c
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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 mu beta estimated for a tetraalkyl-substituted 4-quinopyran, the full AM1-optimized interplanar dihedral angle of which is 104 degrees, is similar to 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'-(dimethyIamino)-4'-nihostilbene, 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 degrees, when the molecule can be described as two disjoint pi-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.
引用
收藏
页码:11174 / 11181
页数:8
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