Method to Derive Restoring Forces of Strained Molecules from Kinetic Measurements

被引：76

作者：

Huang, Zhen ^{[1
]}

Yang, Qing-Zheng ^{[1
]}

Khvostichenko, Daria ^{[1
]}

Kucharski, Timothy J. ^{[1
]}

Chen, Joseph ^{[1
]}

Boulatov, Roman ^{[1
]}

机构：

[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 04期

基金：

美国国家科学基金会;

关键词：

STILBENE;

D O I：

10.1021/ja807113m

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report a method to estimate the restoring force of a constrained small molecule and relate changes in its reactivity to this force. Restoring force is a size-invariant measure of molecular strain and offers a conceptual framework to bridge studies of macromolecular reactions by force spectroscopies with those of strained small molecules. We illustrate our method by showing that E stiff stilbene (1, 1'-Delta-biindan) with up to 700 pN of force along its C6,C6' axis is accessible by photoisomerization. It reverts thermally to the Z isomer with tau(1/2) similar to 100 ms, probably tong enough to be useful for microscale actuation. The quantum yield of photoisomerization and the activation barrier of thermal isomerization of constrained stiff stilbene increase sharply as the restoring force decreases.

引用

页码：1407 / +

页数：4

共 10 条

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