Haketa Yohei, Nakajima Ryoya, Maruyama Yuto, Tanaka Hiroki, Choi Wookjin, Seki Shu, Sato Shunsuke, Baba Hitomi, Ishii Yoshiki, Watanabe Go, Bulgarevich Kirill, Takimiya Kazuo, Deguchi Kenzo, Ohki Shinobu, Hashi Kenjiro, Nakanishi Takashi, Ishibashi Yukihide, Asahi Tsuyoshi, Ohta Kazuchika, Maeda Hiromitsu
Department of Applied Chemistry, College of Life Sciences, Ritsumeikan University Kusatsu 525-8577 Japan
Department of Molecular Engineering, Graduate School of Engineering, Kyoto University Kyoto 615-8510 Japan.
Chem Sci. 2025 Feb 19;16(12):4998-5006. doi: 10.1039/d4sc07576e. eCollection 2025 Mar 19.
Independently stacked positively and negatively charged π-electronic systems in charge-segregated columnar structures are desired for electronic properties derived from their electron-deficient and -rich assembling states, respectively. An expanded π-electronic cation, benzoporphyrin Au complex, was synthesized as the component of ion pairs in combination with counteranions. In contrast to benzoporphyrin, which is known for its insolubility in organic solvents, the ion pairs with bulky anions in this study are soluble in common organic solvents. The ion pairs formed charge-segregated assemblies as two pseudo-polymorphs of single-crystal and less-crystalline (LeC) states based on the stacking of the benzoporphyrin Au complex. XRD and solid-state NMR measurements, along with molecular dynamics (MD) simulation, revealed that the LeC states were formed by a less-ordered arrangement of constituting ions induced by bulky counteranions. The electric conductivity properties were observed in the single-crystal and LeC charge-segregated assemblies.
对于电荷分离的柱状结构中独立堆叠的带正电和负电的π电子体系，分别因其缺电子和富电子组装态而具有的电子性质是人们所期望的。一种扩展的π电子阳离子——苯并卟啉金配合物，被合成出来作为与抗衡阴离子形成离子对的组分。与以在有机溶剂中不溶而闻名的苯并卟啉不同，本研究中带有大体积阴离子的离子对可溶于常见有机溶剂。基于苯并卟啉金配合物的堆叠，这些离子对形成了电荷分离的组装体，呈现出单晶和少晶（LeC）态这两种假多晶型。X射线衍射（XRD）和固态核磁共振（NMR）测量，以及分子动力学（MD）模拟表明，LeC态是由大体积抗衡阴离子诱导的构成离子的无序排列形成的。在单晶和LeC电荷分离组装体中观察到了导电性能。
