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Construction of a Metal‐Free Electron Spin System by Encapsulation of an NO Molecule Inside an Open‐Cage Fullerene C 60 Derivative
Author(s) -
Hasegawa Shota,
Hashikawa Yoshifumi,
Kato Tatsuhisa,
Murata Yasujiro
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201807823
Subject(s) - paramagnetism , fullerene , chemistry , molecule , electron paramagnetic resonance , cage , crystallography , metal , derivative (finance) , photochemistry , nuclear magnetic resonance , condensed matter physics , organic chemistry , financial economics , economics , physics , mathematics , combinatorics
A reactive radical species, nitric oxide (NO), was encapsulated in a unimolecular form inside an open‐cage fullerene derivative under high‐pressure conditions in the solid state. Surprisingly, the molecular complex showed sharp 1 H NMR signals despite the existence of the paramagnetic species inside the carbon cage. Owing to the paramagnetic shifts, the escape rate of the NO was determined experimentally. After constructing a stopper on the rim of the opening, the NO was found to stay inside the cage even at 50 °C. The ESR measurements of the powdery sample showed paramagnetic properties at low temperature. The single‐crystal X‐ray structure analysis clearly demonstrated the existence of the encapsulated NO molecule, suggesting rapid rotation inside the cage. The 1 H NMR chemical shifts displayed a large temperature dependence owing to the paramagnetic effects.