The Unanticipated Dimerization of Ce@C-2v(9)-C-82 upon Co-crystallization with Ni(octaethylporphyrin) and Comparison with Monomeric M@C-2v(9)-C-82 (M = La, Sc, and Y)

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F16%3A10332104" target="_blank" >RIV/00216208:11310/16:10332104 - isvavai.cz</a>

Result on the web

<a href="http://dx.doi.org/10.1002/chem.201602595" target="_blank" >http://dx.doi.org/10.1002/chem.201602595</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.201602595" target="_blank" >10.1002/chem.201602595</a>

Result language

angličtina

Original language name

The Unanticipated Dimerization of Ce@C-2v(9)-C-82 upon Co-crystallization with Ni(octaethylporphyrin) and Comparison with Monomeric M@C-2v(9)-C-82 (M = La, Sc, and Y)

Original language description

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.

Czech name

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Czech description

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Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

CF - Physical chemistry and theoretical chemistry

OECD FORD branch

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Project

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Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2016

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

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Volume of the periodical

22

Issue of the periodical within the volume

50

Country of publishing house

DE - GERMANY

Number of pages

8

Pages from-to

18115-18122

UT code for WoS article

000390604600036

EID of the result in the Scopus database

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