From Wires to Cables: Attempted Synthesis of 1,3,5-Trifluorenylcyclohexane as a Platform for Molecular Cables
From Wires to Cables: Attempted Synthesis of 1,3,5-Trifluorenylcyclohexane as a Platform for Molecular Cables
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从电线到电缆：尝试合成 1,3,5-三芴基环己烷作为分子电缆的平台
DOI：
10.1021/acs.joc.5b02792
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
Rathore, Rajendra
中科院分区：
文献类型：
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作者：
Talipov, Marat R.;Abdelwahed, Sameh H.;Thakur, Khushabu;Reid, Scott A.;Rathore, Rajendra
多个分子线编织在一起的一个单一的组件，被称为分子电缆，是有前途的下一代材料的有效的远程电荷传输。以1，3，5-三芴基环己烷（TFC）及其二芴基类似物（DFCs）为例，从实验（X射线晶体学）和理论（DFT计算）两个方面系统地研究了分子电缆的构建平台.虽然DFC的合成成功地实现了，但TFC的合成，其涉及与最后一步类似的分子内Friedel-Crafts环化，是不成功的。一个详尽的研究的构象景观的环己烷环的TFCandDFCs显示，TFCs是一个适度应变的分子（约17千卡/摩尔），和计算研究的反应概况表明，这种空间应变，目前在过渡态，是负责异常高（约15年）的反应半衰期。一个成功的合成ofTFC将需要立体应变引入多个步骤，目前正在探索这样的替代策略。
Multiple molecular wires braided together in a single assembly, termed as molecular cable, are promising next-generation materials for effective long-range charge transport. As an example of the platform for constructing molecular cables, 1,3,5-trifluorenylcyclohexane (TFC) and its difluorenyl analogues (DFCs) were systematically investigated both experimentally (X-ray crystallography) and theoretically (DFT calculations). Although the syntheses ofDFCs were successfully achieved, the synthesis ofTFC, which involved a similar intramolecular Friedel–Crafts cyclization as the last step, was unsuccessful. An exhaustive study of the conformational landscape of cyclohexane ring ofTFCandDFCs revealed thatTFCis a moderately strained molecule (∼17 kcal/mol), and computational studies of the reaction profile show that this steric strain, present in the transition state, is responsible for the unusually high (∼5 years) reaction half-life. A successful synthesis ofTFCwill require that the steric strain is introduced in multiple steps, and such alternative strategies are being currently explored.