Two missing cage isomers of C_(86)have been successfully stabilized by the encapsulation of the actinide ion Th.The two novel isomers of Th@C_(86)were synthesized using the arc-discharge method and characterized using...Two missing cage isomers of C_(86)have been successfully stabilized by the encapsulation of the actinide ion Th.The two novel isomers of Th@C_(86)were synthesized using the arc-discharge method and characterized using mass spectrometry,single-crystal X-ray crystallography,UV-vis-NIR spectroscopy and DFT calculations.The molecular structures of the two isomers were unambiguously assigned to Th@C_(2)(14)-C_(86)and Th@C_(3)(18)-C_(86)by crystallographic analysis.Both of these cage isomers of C_(86)have been predicted by computational studies but have never been experimentally confirmed until now.DFT computation reveals that both Th@C_(2)(14)-C_(86)and Th@C_(3)(18)-C_(86)present closed-shell electronic configurations with formally Th(Ⅳ),consistent with other previously reported Th based mono-metallofullerenes.Th@C_(2)(14)-C_(86)has emerged as the third lowest-energy isomer with significant predicted abundance at temperatures of fullerene formation.Th@C_(3)(18)-C_(86),on the other hand,represents an unexpected isomer with low thermodynamic stability,but significant abundance.Its formation was further rationalized as a kinetically trapped intermediate obtained from the lowest-energy and abundant Th@C_(2)(8)-C_(84),by a C_(2)insertion and a single Stone-Wales transformation.This study highlights the unique impact of actinides on the stabilization of fullerene cage isomers and also provides a more in-depth understanding into the stabilization mechanism of fullerene cage isomers.展开更多
基金National Natural Science Foundation of China(NSFC no.52172051)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)+1 种基金the Spanish Ministry of Science and Innovation(grant PID2020-112762GB-I00 funded by MCIN/AEI/10.13039/501100011033)the Generalitat de Catalunya(grant 2021SGR00110)and the URV for support.
文摘Two missing cage isomers of C_(86)have been successfully stabilized by the encapsulation of the actinide ion Th.The two novel isomers of Th@C_(86)were synthesized using the arc-discharge method and characterized using mass spectrometry,single-crystal X-ray crystallography,UV-vis-NIR spectroscopy and DFT calculations.The molecular structures of the two isomers were unambiguously assigned to Th@C_(2)(14)-C_(86)and Th@C_(3)(18)-C_(86)by crystallographic analysis.Both of these cage isomers of C_(86)have been predicted by computational studies but have never been experimentally confirmed until now.DFT computation reveals that both Th@C_(2)(14)-C_(86)and Th@C_(3)(18)-C_(86)present closed-shell electronic configurations with formally Th(Ⅳ),consistent with other previously reported Th based mono-metallofullerenes.Th@C_(2)(14)-C_(86)has emerged as the third lowest-energy isomer with significant predicted abundance at temperatures of fullerene formation.Th@C_(3)(18)-C_(86),on the other hand,represents an unexpected isomer with low thermodynamic stability,but significant abundance.Its formation was further rationalized as a kinetically trapped intermediate obtained from the lowest-energy and abundant Th@C_(2)(8)-C_(84),by a C_(2)insertion and a single Stone-Wales transformation.This study highlights the unique impact of actinides on the stabilization of fullerene cage isomers and also provides a more in-depth understanding into the stabilization mechanism of fullerene cage isomers.
