Studies on the Bridge Dependence of Bis(triarylamine) Diradical Dications: Long-Range π-Conjugation and π–π Coupling Systems,The Journal of Organic Chemistry

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Studies on the Bridge Dependence of Bis(triarylamine) Diradical Dications: Long-Range π-Conjugation and π–π Coupling Systems
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2018-03-06 00:00:00 , DOI: 10.1021/acs.joc.8b00003
Shuyu Li ₁ , Ningning Yuan ₁ , Yong Fang ₁ , Chao Chen ₁ , Lei Wang ₁ , Rui Feng ₁ , Yue Zhao ₁ , Haiyan Cui _{1,

2} , Xinping Wang ₁

Affiliation

Three bis(triarylamine) dications bridged with 2,2′-bithienyl group (1²⁺), biphenyl group (2²⁺) and [2,2]paracyclophane (3²⁺) have been successfully isolated. The electronic structures of 1²⁺ – 3²⁺ show bridge dependence. Magnetic studies and DFT calculations show that dications 1²⁺ – 3²⁺ possess an open-shell singlet ground state with a thermally excited triplet state. Dication 3²⁺ has rather small singlet–triplet energy gap and could basically be regarded as a nearly pure diradical. Diradical dications 1²⁺ – 3²⁺ represent rare examples of diradicaloids with intramolecular long-range π-conjugation or π–π coupling interaction.

中文翻译：

双（三芳基胺）双自由基阳离子的桥依赖性研究：远程π共轭和π–π耦合系统

已成功分离了3,2,2'-联噻吩基（1 ²⁺），联苯基（2 ²⁺）和[2,2]对环环烷（3 ²⁺）桥接的双（三芳基胺）阳离子。1 ²⁺ – 3 ²⁺的电子结构显示出电桥依赖性。磁性研究和DFT计算表明，药1 ²⁺ – 3 ²⁺具有开壳单重态和热激发三重态。Dication 3 ²⁺具有相当小的单重态-三重态能隙，基本上可以看作是几乎纯的双自由基。根治性适应症1²⁺ – 3 ²⁺代表双自由基类化合物在分子内长距离π共轭或π–π耦合相互作用的罕见例子。

更新日期：2018-03-06

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