Ho2O@D-3(85)-C-92: Highly Stretched Cluster Dictated by a Giant Cage and Unexplored Isomerization

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F20%3A10419524" target="_blank" >RIV/00216208:11310/20:10419524 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=da0byBRuPH" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=da0byBRuPH</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.0c01512" target="_blank" >10.1021/acs.inorgchem.0c01512</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Ho2O@D-3(85)-C-92: Highly Stretched Cluster Dictated by a Giant Cage and Unexplored Isomerization

Popis výsledku v původním jazyce

For endohedral metallofullerenes (EMFs), it has been well established that the cage shape and size should match those of the endohedral cluster. As a result, sufficient cluster-cage interaction can be achieved, which is essential for mutual stabilization. Nevertheless, how a small endohedral cluster nests in a giant fullerene has been less explored. Herein, we report a pair of large oxide-cluster fullerene (OCF) isomers, denoted as Ho2O@C-92-I and -II. Crystallographic studies reveal that major isomer-I possesses a D-3(85)-C-92 cage with a highly stretched Ho2O cluster inside, which contributes to achieving regular metal-cage contacts. Density functional theory (DFT) computations also reveal the predominant abundance of the D-3(85) isomer relative to the other two possible minor species including C-1(67) and C-2(64) isomers. Moreover, electrochemical (EC) studies verify that the isomers exhibit almost identical redox behaviors, indicating their similar cage structures. On the basis of the remarkable topological similarity of D-3(85) and C-1(67) isomers, isomer-II is likely to be Ho2O@C-1(67)-C-92, though it remains to be confirmed. Our studies thus provide new insights into the cage-cluster interplay and cage isomerization, both contributing to a better understanding of large EMFs.

Název v anglickém jazyce

Ho2O@D-3(85)-C-92: Highly Stretched Cluster Dictated by a Giant Cage and Unexplored Isomerization

Popis výsledku anglicky

For endohedral metallofullerenes (EMFs), it has been well established that the cage shape and size should match those of the endohedral cluster. As a result, sufficient cluster-cage interaction can be achieved, which is essential for mutual stabilization. Nevertheless, how a small endohedral cluster nests in a giant fullerene has been less explored. Herein, we report a pair of large oxide-cluster fullerene (OCF) isomers, denoted as Ho2O@C-92-I and -II. Crystallographic studies reveal that major isomer-I possesses a D-3(85)-C-92 cage with a highly stretched Ho2O cluster inside, which contributes to achieving regular metal-cage contacts. Density functional theory (DFT) computations also reveal the predominant abundance of the D-3(85) isomer relative to the other two possible minor species including C-1(67) and C-2(64) isomers. Moreover, electrochemical (EC) studies verify that the isomers exhibit almost identical redox behaviors, indicating their similar cage structures. On the basis of the remarkable topological similarity of D-3(85) and C-1(67) isomers, isomer-II is likely to be Ho2O@C-1(67)-C-92, though it remains to be confirmed. Our studies thus provide new insights into the cage-cluster interplay and cage isomerization, both contributing to a better understanding of large EMFs.

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

2020

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

59

Číslo periodika v rámci svazku

15

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

8

Strana od-do

11020-11027

Kód UT WoS článku

000558727500064

EID výsledku v databázi Scopus

2-s2.0-85088364573