Polyynes as a model for carbyne: Synthesis, physical properties, and nonlinear optical response

被引:360
作者
Eisler, S
Slepkov, AD
Elliott, E
Luu, T
McDonald, R
Hegmann, FA [1 ]
Tykwinski, RR
机构
[1] Univ Alberta, Dept Chem, Edmonton, AB T6G 2G2, Canada
[2] Univ Alberta, Dept Phys, Edmonton, AB T6G 2J1, Canada
关键词
D O I
10.1021/ja044526l
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
With the Fritsch-Buttenberg-Wiechell rearrangement as a primary synthetic route, a series of conjugated, triisopropylsilyl end-capped polyynes containing 2-10 acetylene units has been assembled. In a few steps, significant quantities of the polyynes are made available, which allow for a thorough analysis of their structural, physical, and optical properties. Molecules in the series have been characterized in detail using C-13 NMR spectroscopy, differential scanning calorimetry, mass spectrometry, and, for four derivatives including octayne 6, X-ray crystallography. UV-vis spectroscopy of the polyynes 1-7 shows a consistent lowering of the HOMO-LUMO gap (E-g) as a function of the number of acetylene units (n), fitting a power-law relationship of E-g similar to n(-0.379+0.002). The third-order nonlinear optical (NLO) properties of the polyyne series have been examined, and the nonresonant molecular second hyperpolarizabilities (gamma) increase as a function of length according to the power-law gamma similar to n(4.28+/-0.13). This result exhibits an exponent that is larger than theoretically predicted for polyynes and higher than is observed for polyenes and polyenynes. The combined linear and nonlinear optical results confirm recent theoretical studies that suggest polyynes as model 1-D conjugated systems. On the basis of UV-vis spectroscopic analysis, the effective conjugation length for this series of polyynes is estimated to be ca. n = 32, providing insight into characteristics of carbyne.
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页码:2666 / 2676
页数:11
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