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871.
Yasuyuki Yamada Hiroaki Nakajima Chisa Kobayashi Yoshiaki Shuku Kunio Awaga Shigehisa Akine Kentaro Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2023,29(1):e202203272
A C4h symmetrically substituted phthalocyanine, 1,8,15,22-tertrakis(2,4-dimethylpent-3-oxy)phthalocyanine (H2TdMPPc), was used to synthesize Tb3+-phthalocyanine double-decker complexes ([Tb(TdMPPc)2]s). Because H2TdMPPc has C4h symmetry, S,S, R,R, and meso isomers of [Tb(TdMPPc)2] were obtained depending on the difference in the direction of the coordination plane of two C4h-type phthalocyanines with respect to a central Tb3+ ion. We investigated the physical properties of these [Tb(TdMPPc)2] isomers, including their single-ion magnetic properties, and found that the spin-reversal energy barrier (Ueff) of the meso isomer was apparently higher than that of the enantiomers. Detailed crystal structural analyses indicated that the meso isomer has a more symmetrical structure than do the enantiomers, thereby suggesting that the higher Ueff of the meso isomer originated from the more highly symmetrical structure. 相似文献
872.
873.
Bat-El Oded Yael Diskin-Posner Dr. Vered Marks Prof. Haya Kornweitz Prof. Flavio Grynszpan 《European journal of organic chemistry》2023,26(39):e202300697
Theoretical and experimental mixed approaches are complementary and valuable. Our DFT calculations support the mechanism suggested by Kosower, adding to it a key diaziridine intermediate that determines the relative product distribution of this reaction. Our results are consistent with the formation of the diazoketene intermediate as the rate-limiting step. Based on curve fittings, first or second-order kinetics cannot be ruled out. This may indicate that more than one mechanism is simultaneously at play in this transformation. This unexpected outcome led us to study an alternative cyclopropenone intermediate. Although cyclopropenone is not likely to be formed under thermal conditions, adding it to the reaction mixture results in bimane structures. The most staggering finding from this investigation was the unanticipated generation of the unsymmetrical anti-(Me,Me)(Ph,Ph)bimane. The optimization of this route towards unsymmetrical bimanes will require additional investigation. 相似文献
874.
875.
利用低温超高真空扫描隧道显微镜对单个钴酞菁分子实现了选键化学反应.通过对吸附于Au(111)表面的单个钴酞菁分子外围H原子的"剪裁",并用实验图像和谱学方法,结合第一性原理理论计算研究了逐步去除钴酞菁分子8个外围H原子的过程.理论计算结果再现了实验中所观测到的分子空间构型的变化,并阐明了吸附体系中局域自旋的恢复和变化过程. 相似文献