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Derivatives of Ce@C(82)(C(2v)) have been synthesized and fully characterized, and their anisotropic magnetism has been observed as paramagnetic shifts in NMR measurements. Carbene addition by photochemical reaction afforded two isomers of Ce@C(82)(C(2v))Ad (Ad = adamantylidene), 2a and 2b, demonstrating high regioselectivity. The two isomers were characterized using MALDI-TOF mass spectrometry, vis-NIR absorption spectroscopy, (1)H and (13)C NMR spectroscopy, and electrochemistry. The structure of the minor isomer (2b) was elucidated by single-crystal X-ray structural analysis. (13)C and (1)H NMR measurements revealed the characteristic anisotropic interaction between the f electron on the Ce atom and nuclear spins of the carbon atoms of the cage and the protons of the Ad group, respectively.
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Takano et al. (2009) studied this question.
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