Three-dimensional nonlinear optical chromophores based on through-space delocalization

被引:121
作者
Bartholomew, GP
Ledoux, I
Mukamel, S
Bazan, GC [1 ]
Zyss, J
机构
[1] Univ Calif Santa Barbara, Dept Chem, Inst Polymers & Organ Solids, Santa Barbara, CA 93106 USA
[2] Univ Calif Santa Barbara, Dept Mat, Inst Polymers & Organ Solids, Santa Barbara, CA 93106 USA
[3] Ecole Normale Super, CNRS, UMR 8537, Lab Photon Quant & Mol, F-94235 Cachan, France
[4] Univ Rochester, Dept Chem, Rochester, NY 14627 USA
关键词
D O I
10.1021/ja0272179
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Six permutations of 4-fold donor and/or acceptor substitution of paracyclophane at the 4, 7, 12, and 15 positions were synthesized to probe the phenomenon of three-dimensional delocalization on the nonlinear optical properties of organic materials. The interplay between through-bond intramolecular charge transfer (ICT) as well as three-dimensional, or through-space, ICT processes gives rise to large quadratic hyperpolarizability values. The determination of dipolar (beta(J=1)) and octupolar (beta(J=3)) irreducible tensor contributions to the overall P tensor value is made possible by the polarized harmonic light scattering technique at 1.32 mum. The electric field-induced second-harmonic generation technique was also used at 1.91 mum for comparison. Significant experimental beta values for members of the, series made of two centrosymmetric benzene-like units are a clear signature of a purely through-space ICT between two aryl subunits. The two configurational isomers that pair two dipolar donor-acceptor chromophores also exhibit octupolar character. Analysis of these two with an additive model for beta(J=1) and P-J=3 reveals a strong three-dimensional inter-ring charge transfer.
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页码:13480 / 13485
页数:6
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