Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore, Singapore.
Department of Materials Science and Engineering, National University of Singapore, 119260, Singapore, Singapore.
Angew Chem Int Ed Engl. 2017 Nov 27;56(48):15383-15387. doi: 10.1002/anie.201709537. Epub 2017 Oct 24.
π-Conjugated molecular cages are very challenging targets in structural organic chemistry, supramolecular chemistry, and materials science. The synthesis and physical characterizations are reported of the first three-dimensionally π-conjugated diradical molecular cage PTM-C, in which two polychlorotriphenylmethyl (PTM) radicals are linked by three bis(3,6-carbazolyl) bridges. This cage compound was synthesized mainly by intermolecular Yamamoto coupling followed by deprotonation and oxidation. It is stable and its structure was confirmed by X-ray crystallographic analysis. The two carbon-centered PTM radicals are weakly coupled through electronic interactions with the carbazole spacers, as revealed by optical, electronic, and magnetic measurements as well as theoretical calculations.
π 共轭分子笼是结构有机化学、超分子化学和材料科学中极具挑战性的目标。本文报道了首例三维 π 共轭双自由基分子笼 PTM-C 的合成和物理性质，其中两个多氯三苯甲基 (PTM) 自由基通过三个双(3,6-咔唑基)桥连接。该笼状化合物主要通过分子间 Yamamoto 偶联，然后脱质子化和氧化合成。它是稳定的，其结构通过 X 射线晶体学分析得到证实。两个碳中心的 PTM 自由基通过与咔唑间隔基的电子相互作用弱耦合，这一点通过光学、电子和磁测量以及理论计算得到了揭示。
