Extremely Long Lived Localized Singlet Diradicals in a Macrocyclic Structure: A Case Study on the Stretch Effect,Chemistry - A European Journal

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Extremely Long Lived Localized Singlet Diradicals in a Macrocyclic Structure: A Case Study on the Stretch Effect
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2018-09-06 , DOI: 10.1002/chem.201803076
Yuta Harada ₁ , Zhe Wang ₁ , Shunsuke Kumashiro ₁ , Sayaka Hatano ₁ , Manabu Abe _{1,

2}

Affiliation

Localized singlet diradicals have attracted much attention, not only in the field of bond‐homolysis chemistry, but also in nonlinear optical materials. In this study, an extremely long lived localized singlet diradical was obtained by using a new molecular design strategy in which it is kinetically stabilized by means of a macrocycle that increases the molecular strain of the corresponding σ‐bonded compound. Notably, the lifetime of this diradical (14 μs) is two orders of magnitude longer than that of a standard singlet diradical without a macrocyclic structure (≈0.2 μs) at 293 K. The species is persistent below a temperature of 100 K. In addition to the kinetic stabilization of the singlet diradical, the spontaneous oxidation of its corresponding ring‐closed compound at 298 K produced oxygenated products under atmospheric conditions. Apparently, the “stretch effect” induced by the macrocyclic structure plays a crucial role in extending the lifetime of localized singlet diradicals and increasing the reactivity of their corresponding σ‐bonded compounds.

中文翻译：

大环结构中的超长寿命局部单线双基自由基：以拉伸效应为例

局部单线双基自由基不仅在键-热解化学领域，而且在非线性光学材料领域都引起了广泛的关注。在这项研究中，通过使用新的分子设计策略获得了寿命极长的局部单线双基自由基，该策略通过大环增加了相应σ键合化合物的分子应变，从而使其动力学稳定。值得注意的是，在293 K下，该双自由基的寿命（14μs）比没有大环结构的标准单线双自由基（≈0.2μs）的寿命长两个数量级。该物种在100 K的温度下仍具有持久性。对于单线双自由基的动力学稳定性，其相应的闭环化合物在298 K下的自发氧化在大气条件下产生了氧化产物。显然，

更新日期：2018-09-06

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