Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 22, Issue 50, Pages 18115-18122Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201602595
Keywords
cage compounds; crystal growth; dimerization; metallofullerenes; structure elucidation
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Funding
- Ministry of Education, Culture, Sports, Science, and Technology of Japan [20108001, 202455006, 24350019, 22000009]
- US National Science Foundation [CHE-1305125]
- Direct For Mathematical & Physical Scien [1305125] Funding Source: National Science Foundation
- Division Of Chemistry [1305125] Funding Source: National Science Foundation
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We report that Ce@C-2v(9)-C-82 forms a centrosymmetric dimer when co-crystallized with Ni(OEP) (OEP = octaethylporphyrin dianion). The crystal structure of {Ce@C-2v(9)-C-82}(2)center dot 2[Ni(OEP)]center dot 4C(6)H(6) shows that a new C-C bond with a bond length of 1.605(5) angstrom connects the two cages. The high spin density of the singly occupied molecular orbital (SOMO) on the cage and the pyramidalization of the cage are factors that favor dimerization. In contrast, the treatment of Ni(OEP) with M@C-2v(9)-C-82 (M = La, Sc, and Y) results in crystallization of monomeric endohedral fullerenes. A systematic comparison of the X-ray structures of M@C-2v(9)-C-82 (M = Sc, Y, La, Ce, Gd, Yb, and Sm) reveals that the major metal site in each case is located at an off-center position adjacent to a hexagonal ring along the C-2 axis of the C-2v(9)-C-82 cage. DFT calculations at the M06-2X level revealed that the positions of the metal centers in these metallofullerenes M@C-2v(9)-C-82 (M = Sc, Y, and Ce), as determined by single-crystal X-ray structure studies, correspond to an energy minimum for each compound.
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