氧杂丙叉基暴露：一种开壳单重态，在溶液中具有皮秒级的寿命，但在环丁烷二酮前体的晶体中持久存在。
Oxyallyl exposed: an open-shell singlet with picosecond lifetimes in solution but persistent in crystals of a cyclobutanedione precursor.
机构信息
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1559, USA.
出版信息
J Am Chem Soc. 2011 Mar 2;133(8):2342-5. doi: 10.1021/ja109494b. Epub 2011 Feb 7.
Abstract
Photoinduced decarbonylation of 2,4-bis(spirocyclohexyl)-1,3-cyclobutanedione 1 in the crystalline solid state resulted in formation of a deep blue transient with λ(max) = 550 nm and a half-life of 42 min at 298 K, identified as kinetically stabilized oxyallyl. Support for an open-shell singlet species was obtained by spectroscopic analysis and (4/4) CASSCF calculations with the 6-31+G(d) basis set and multireference MP2 corrections. The electronic spectrum of the singlet biradical, confirmed by femtosecond pump-probe studies in solution, was matched by coupled cluster calculations with single and double corrections.
摘要
在 298 K 下，晶体固态中的 2,4-双（螺环环己基）-1,3-环丁二酮 1 的光诱导脱羰反应生成了一个具有 λ(max) = 550nm 和半衰期为 42 分钟的深蓝色瞬态物质，被鉴定为动力学稳定的氧杂丙二烯。通过光谱分析和（4/4）CASSCF 计算（使用 6-31+G(d)基组和多参考 MP2 校正）获得了开壳单重态物种的支持。通过溶液中飞秒泵浦探测研究证实了单重态双自由基的电子光谱，并用带有单重和双重校正的耦合簇计算进行了匹配。
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