Isolation and Crystallographic Characterization of the Labile Isomer of Y@C-82 Cocrystallized with Ni(OEP): Unprecedented Dimerization of Pristine Metallofullerenes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F16%3A10332115" target="_blank" >RIV/00216208:11310/16:10332115 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1002/anie.201604121" target="_blank" >http://dx.doi.org/10.1002/anie.201604121</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/anie.201604121" target="_blank" >10.1002/anie.201604121</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Isolation and Crystallographic Characterization of the Labile Isomer of Y@C-82 Cocrystallized with Ni(OEP): Unprecedented Dimerization of Pristine Metallofullerenes

Popis výsledku v původním jazyce

Although the major isomers of M@C-82 (namely M@C-2v(9)-C-82, where M is a trivalent rare-earth metal) have been intensively investigated, the lability of the minor isomers has meant that they have been little studied. Herein, the first isolation and crystallographic characterization of the minor Y@C-82 isomer, unambiguously assigned as Y@Cs(6)-C-82 by cocrystallization with Ni(octaethylporphyrin), is reported. Unexpectedly, a regioselective dimerization is observed in the crystalline state of Y@Cs(6)-C-82. In sharp contrast, no dimerization occurs for the major isomer Y@C-2v(9)-C-82 under the same conditions, indicating a cage-symmetry-induced dimerization process. Further experimental and theoretical results disclose that the regioselective dimer formation is a consequence of the localization of high spin density on a special cage-carbon atom of Y@Cs(6)-C-82 which is caused by the steady displacement of the Yatom inside the Cs(6)-C-82 cage.

Název v anglickém jazyce

Isolation and Crystallographic Characterization of the Labile Isomer of Y@C-82 Cocrystallized with Ni(OEP): Unprecedented Dimerization of Pristine Metallofullerenes

Popis výsledku anglicky

Although the major isomers of M@C-82 (namely M@C-2v(9)-C-82, where M is a trivalent rare-earth metal) have been intensively investigated, the lability of the minor isomers has meant that they have been little studied. Herein, the first isolation and crystallographic characterization of the minor Y@C-82 isomer, unambiguously assigned as Y@Cs(6)-C-82 by cocrystallization with Ni(octaethylporphyrin), is reported. Unexpectedly, a regioselective dimerization is observed in the crystalline state of Y@Cs(6)-C-82. In sharp contrast, no dimerization occurs for the major isomer Y@C-2v(9)-C-82 under the same conditions, indicating a cage-symmetry-induced dimerization process. Further experimental and theoretical results disclose that the regioselective dimer formation is a consequence of the localization of high spin density on a special cage-carbon atom of Y@Cs(6)-C-82 which is caused by the steady displacement of the Yatom inside the Cs(6)-C-82 cage.

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

Angewandte Chemie - International Edition

ISSN

1433-7851

e-ISSN

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Svazek periodika

55

Číslo periodika v rámci svazku

32

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

5

Strana od-do

9234-9238

Kód UT WoS článku

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EID výsledku v databázi Scopus

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