Isolation and Structural Characterization of Er@C-2v(9)-C-82 and Er@C-s(6)-C-82: Regioselective Dimerization of a Pristine Endohedral Metallofullerene Induced by Cage Symmetry

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F19%3A10403724" target="_blank" >RIV/00216208:11310/19:10403724 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=G4p1w-aL2r" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=G4p1w-aL2r</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.8b03313" target="_blank" >10.1021/acs.inorgchem.8b03313</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Isolation and Structural Characterization of Er@C-2v(9)-C-82 and Er@C-s(6)-C-82: Regioselective Dimerization of a Pristine Endohedral Metallofullerene Induced by Cage Symmetry

Popis výsledku v původním jazyce

Two Er@C-82 isomers have been isolated and unambiguously characterized as Er@C-2v(9)-C-82 and Er@C-s(6)-C-82, respectively, by single-crystal X-ray diffraction. Er@C-s(6)-C-82 is identified as a dimeric structure in the crystalline state, but dimerization does not occur for Er@C-2v(9)-C-82 under identical crystallization conditions, indicating a cage-symmetry-induced dimerization process. Density functional theory calculations reveal that the major unpaired spin resides on a special C atom of Er@C-s(6)-C-82, which leads to regioselective dimerization. Calculations also found that the dimeric structure of Er@C-s(6)-C-82 center dot Ni(OEP) is much more stable than the two monomers, suggesting a thermodynamically favorable dimerization process. Vis-near-IR spectrometric and electrochemical results demonstrate that the electronic structure of Er@C-82 isomers is Er3+@C-82(3-), instead of the theoretically proposed Er2+@C-82(2-).

Název v anglickém jazyce

Isolation and Structural Characterization of Er@C-2v(9)-C-82 and Er@C-s(6)-C-82: Regioselective Dimerization of a Pristine Endohedral Metallofullerene Induced by Cage Symmetry

Popis výsledku anglicky

Two Er@C-82 isomers have been isolated and unambiguously characterized as Er@C-2v(9)-C-82 and Er@C-s(6)-C-82, respectively, by single-crystal X-ray diffraction. Er@C-s(6)-C-82 is identified as a dimeric structure in the crystalline state, but dimerization does not occur for Er@C-2v(9)-C-82 under identical crystallization conditions, indicating a cage-symmetry-induced dimerization process. Density functional theory calculations reveal that the major unpaired spin resides on a special C atom of Er@C-s(6)-C-82, which leads to regioselective dimerization. Calculations also found that the dimeric structure of Er@C-s(6)-C-82 center dot Ni(OEP) is much more stable than the two monomers, suggesting a thermodynamically favorable dimerization process. Vis-near-IR spectrometric and electrochemical results demonstrate that the electronic structure of Er@C-82 isomers is Er3+@C-82(3-), instead of the theoretically proposed Er2+@C-82(2-).

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2019

Kód důvěrnosti údajů

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

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

—

Svazek periodika

58

Číslo periodika v rámci svazku

3

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

6

Strana od-do

2177-2182

Kód UT WoS článku

000458085900051

EID výsledku v databázi Scopus

2-s2.0-85061031920