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)

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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)

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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)

Popis výsledku anglicky

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.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

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Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2016

Kód důvěrnosti údajů

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

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

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Svazek periodika

22

Číslo periodika v rámci svazku

50

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

8

Strana od-do

18115-18122

Kód UT WoS článku

000390604600036

EID výsledku v databázi Scopus

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