Crystallization-Induced Planar Chirality by Asymmetric Ferrocene-Appended Tetraazanaphthacene
Crystallization-Induced Planar Chirality by Asymmetric Ferrocene-Appended Tetraazanaphthacene
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DOI：
10.1021/acs.cgd.0c00934
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发表时间：
2020-11-04
影响因子：
3.8
通讯作者：
Tadokoro, Makoto
中科院分区：
文献类型：
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作者：
Isoda, Kyosuke;Haga, Harufumi;Tadokoro, Makoto
尽管具有很高的挑战性，但不需要外消旋的自发结晶是一种创新的策略，可以方便地制备具有平面手性的对映选择性聚集体。因此，为了探索这一概念的可行性，我们报道了一种N-杂并苯的分子设计策略，重点是利用供体诱导手性。我们合成了由二茂铁(FC)和四氮杂菲(TANC)组成的不对称供体-受体(D-A)型衍生物FcTANC。溶液状态的H-1核磁共振测量表明，FC和唐之间的单键在核磁共振时间尺度上是自由转动的。单晶X射线分析表明，FcTANC产生了三种晶型，具体地说，一种外消旋和两种对映体。此外，FcTANC的紫外可见吸收光谱有一个来自金属到配体的电荷转移的峰，表现出溶剂变色行为。循环伏安法显示有三个可逆峰，分别来自给电子体Fc和电子接受体TanC。
Although highly challenging, spontaneous crystallization without racemization can be an innovative strategy for the facile preparation of an enantioselective conglomerate with planar chirality. Therefore, to explore the feasibility of this concept, we report a molecular design strategy for an N-heteroacene focusing on inducing chirality using a donor. We synthesized an asymmetric donor-acceptor (D-A)-type derivative, FcTANC, composed of ferrocene (Fc) and tetraazanaphthacene (TANC). Solution-state H-1 NMR measurements revealed the free rotation of the single bond between Fc and TANG on the NMR time scale. Single-crystallographic X-ray analysis revealed that FcTANC generated three types of crystal polymorphs, specifically, one racemic and two enantiometric conglomerates. Also, the UV-visible absorption spectra of FcTANC have a peak derived from the metal-to-ligand charge transfer showing solvatochromic behavior. Cyclic voltammetry showed three reversible peaks derived from electron-donating Fc and electron-accepting TANC.