期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 138, 期 7, 页码 2399-2410出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b13033
关键词
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资金
- JSPS [2615260, 2604505, 25248007, 26288016]
- MEXT [A24109002a, 15H00999, A26107004a, 15H01086]
- Strategic Programs for Innovative Research (SPIRE), MEXT
- Computational Materials Science Initiative (CMSI), Japan
- MEXT, Japan [24109008]
- Grants-in-Aid for Scientific Research [15H01086, 14J01526, 24109008, 15H00999, 26107004, 26288016, 25248007, 24109002] Funding Source: KAKEN
First isolation and characterization of biphenalenylidenes, which have long been unidentified reactive intermediates on the decomposition pathway of phenalenyl radical, were accomplished. Photoinduced electrocyclic ring opening reaction of anti-dihydroperopyrene resulted in a successful conversion to E-biphenalenylidene, which enabled a detailed investigation of the electronic structure of E-biphenalenylidene by means of spectroscopic techniques. A stereoisomer, Z-biphenalenylidene, was also observed by suppressing a facile E-Z isomerization to E-biphenalenylidene in a rigid matrix. Furthermore, Z-biphenalenylidene demonstrated a thermal ring-closure in conrotatory process, which is not conforming to the Woodward Hoffmann rule. These unusual reactivities of biphenalenylidene are ascribed to the ground states destabilized by its singlet biradical character, which was fully supported by theoretical calculations. The presence of E-biphenalenylidene on the decomposition pathway of phenalenyl was confirmed experimentally, leading to the full understanding of the decomposition mechanism of phenalenyl.
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