- Facile Synthesis of a Fully Fused, Three-Dimensional ?-Conjugated Archimedean Cage with Magnetically Shielded Cavity
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The synthesis of molecular cages consisting of fully fused, ?-conjugated rings is rare due to synthetic challenges including preorganization, large strain, and poor solubility. Herein, we report such an example in which a tris-2-aminobenzophenone precursor undergoes acid-mediated self-condensation to form a truncated tetrahedron, one of the 13 Archimedean solids. Formation of eight-membered [1,5]diazocine rings provides preorganization and releases the strain while still maintains weak ?-conjugation of the backbone. Thorough characterizations were performed by X-ray, NMR, and UV-vis analysis, assisted by theoretical calculations. The cage exhibits a rigid backbone structure with a well-defined cavity that confines a magnetically shielded environment. The solvent molecule, o-dichlorobenzene, is precisely encapsulated in the cavity at a 1:1 ratio with multiple ?···?, C-H···?, and halogen···πinteractions with the cage skeleton, implying its template effect for the cage closing reaction. Our synthetic strategy opens the opportunity to access more complex, fully fused, three-dimensional ?-conjugated cages.
- Han, Yi,Jiao, Tianyu,Li, Zhengtao,Ni, Yong,Wu, Jishan,Wu, Shaofei,Zhang, Qiuyu,Zhu, Jun
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supporting information
p. 14314 - 14321
(2021/09/13)
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- Involvement of Exciplexes in the Photolysis of Aliphatic Ketones in Deuteriochloroform: CIDNP Evidence
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Photolysis of 4-acetyl-4-ethoxyformylcyclohexanone and 4-acetyl-4-phenylcyclohexanone in deuteriochloroform showed an unusual polarization which suggests that a singlet exciplex of the ketone with deuteriochloroform may be involved in the Norrish type I reaction.KEY WORDS - Photolysis Ketones CIDNP Exciplex
- Zhang, Mao-Xi,Liu, Zhong-Li,Wu, Lung-Min,Liu, You-Cheng
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p. 451 - 454
(2007/10/02)
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- MICROWAVE SPECTRA AND STRUCTURE OF DICHLOROETHENES
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The complete rs structures for both 1,1- and cis-1,2-dichloroethenes have been derived from isotopic measurements for each isotopic position.The accuracy of the structural parameters obtained is discussed on the basis of isotope effect on bond lengths caused by zero-point vibrations, and it is suggested that more than 0.01 Angstroem of additional uncertainty originating from the isotope effect must be considered for the bond lengths determined by means of the Kraitchman method.The quadrupole coupling constants are re-evaluated by use of the newly determined structures.
- Takeo, Harutoshi,Sugie, Masaaki,Matsumura, Chi
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p. 205 - 214
(2007/10/02)
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