Konarev Dmitri V, Kuzmin Aleksey V, Khasanov Salavat S, Shestakov Alexander F, Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Lyubovskaya Rimma N
Institute of Problems of Chemical Physics, RAS, Chernogolovka, Moscow region, 142432, Russia.
Institute of Solid State Physics, RAS, Chernogolovka Moscow Region, 142432, Russia.
Chem Asian J. 2020 Sep 1;15(17):2689-2695. doi: 10.1002/asia.202000615. Epub 2020 Jul 22.
Two salts of the aromatic hydrocarbon decacyclene, {cryptand2.2.2} (decacyclene ) (1) and {Bu MeP }(decacyclene ) (2), were obtained. In both salts, decacyclene radical anions formed channels occupied by cations. However, corrugated hexagonal decacyclene layers could be outlined in the crystal structure of 1 with several side-by-side C⋅⋅⋅C approaches. The decacyclene radical anions showed strong distortion in both salts, deviating from the C symmetry owing to the repulsion of closely arranged hydrogen atoms and the Jahn-Teller effect. Radical anions showed intense unusually low energy absorption in the IR-range, with maxima at 4800 and 6000 cm . According to the carculations, these bands can originate from the SOMO-LUMO+1 and SOMO-LUMO+2 transitions, respectively. Radical anions exhibited a S=1/2 spin state, with an effective magnetic moment of 1.72 μ at 300 K. The decacyclene spin antiferromagnetically coupled with a Weiss temperature of -11 K. Spin ordering was not observed down to 1.9 K owing to spin frustration in the hexagonal decacyclene layers.
得到了芳香烃并十环烯的两种盐，即{穴醚2.2.2}(并十环烯)(1)和{Bu MeP }(并十环烯)(2)。在这两种盐中，并十环烯自由基阴离子形成了由阳离子占据的通道。然而，在1的晶体结构中可以勾勒出波纹状的六方并十环烯层，其中有几个并排的C⋅⋅⋅C接触。并十环烯自由基阴离子在两种盐中都表现出强烈的畸变，由于紧密排列的氢原子的排斥作用和 Jahn-Teller 效应而偏离 C 对称性。自由基阴离子在红外范围内表现出强烈的异常低能量吸收，最大值分别在4800和6000 cm 处。根据计算，这些谱带分别可源于SOMO-LUMO+1和SOMO-LUMO+2跃迁。自由基阴离子表现出S=1/2的自旋态，在300 K时有效磁矩为1.72 μ。并十环烯自旋通过-11 K的魏斯温度发生反铁磁耦合。由于六方并十环烯层中的自旋受挫，在1.9 K以下未观察到自旋有序。
