Spin-Spin Interactions in One‐Dimensional Assemblies of a Cumulene‐Based Singlet Biradical
Spin-Spin Interactions in One‐Dimensional Assemblies of a Cumulene‐Based Singlet Biradical
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基于积烯的单线态双自由基一维组装中的自旋-自旋相互作用
DOI：
10.1002/anie.202105740
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Kubo Takashi
中科院分区：
文献类型：
--
作者：
Hirao Yasukazu;Daifuku Yoko;Ihara Keiji;Kubo Takashi
描述了非那烯基封端的[5]累积多烯作为基于累积多烯的单重态双自由基的合成以及一维聚集体的自旋相关变化。非那烯基环自聚集的高倾向性和在适当位置引入大体积取代基导致形成一维链组装体。单晶X-射线结构分析表明，随着温度的降低，累积多烯链的键长变化增加，沿着，并改善了非那烯基环的重叠。变温拉曼光谱和磁化率测量表明，分子内的局域自旋对在低温下会发生共振，并且在一维链中出现了涉及分子内和分子间自旋-自旋相互作用的连续自旋系统。
The synthesis of phenalenyl‐endcapped [5]cumulene as a cumulene‐based singlet biradical and the spin correlation changes of one‐dimensional aggregates are described. The high propensity for self‐aggregation of phenalenyl rings and the introduction of bulky substituents into the appropriate positions led to the formation of a one‐dimensional chain assembly. Single‐crystal X‐ray structural analysis indicated that the bond length alternation of the cumulene chain increased with decreasing temperature, along with improved overlapping of the phenalenyl rings. Variable‐temperature Raman spectroscopy and magnetic susceptibility measurements revealed that a localized spin pair within the molecule decouples at low temperatures, and a continuum spin system involving intra‐ and intermolecular spin–spin interactions emerges in the one‐dimensional chain.