Isomeric Sc2O@C-78 Related by a Single-Step Stone-Wales Transformation: Key Links in an Unprecedented Fullerene Formation Pathway

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F16%3A10332098" target="_blank" >RIV/00216208:11310/16:10332098 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.inorgchem.6b01894" target="_blank" >http://dx.doi.org/10.1021/acs.inorgchem.6b01894</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.6b01894" target="_blank" >10.1021/acs.inorgchem.6b01894</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Isomeric Sc2O@C-78 Related by a Single-Step Stone-Wales Transformation: Key Links in an Unprecedented Fullerene Formation Pathway

Popis výsledku v původním jazyce

It has been proposed that the fullerene formation mechanism involves either a top-down or bottom up pathway. Despite different starting points, both mechanisms approve that particular fullerenes or metallofullerenes are formed through a consecutive stepwise process involving Stone-Wales transformations (SWTs) and C-2 losses or additions. However, the formation pathway has seldomly been defined at the atomic level due to the missing-link fullerenes. Herein, we present the isolation and crystallographic characterization of two isomeric clusterfullerenes Sc2O@C-2v(3)-C-78 and Sc2O@D-3h(5)-C-78, which are closely related via a single-step Stone Wales (SW) transformation. More importantly, these novel Sc2O@C-78 isomers represent the key links in a well-defined formation pathway for the majority of solvent-extractable clusterfullerenes Sc2O@C-2n (n = 38-41), providing molecular structural evidence for the less confirmed fullerene formation mechanism. Furthermore, DFT calculations reveal a SWT with a notably low activation barrier for these Sc2O@C-78 isomers, which may rationalize the established fullerene formation pathway. Additional characterizations demonstrate that these Sc2O@C-78 isomers feature different energy bandgaps and electrochemical behaviors, indicating the impact of SW defects on the energetic and electrochemical characteristics of metallofullerenes.

Název v anglickém jazyce

Isomeric Sc2O@C-78 Related by a Single-Step Stone-Wales Transformation: Key Links in an Unprecedented Fullerene Formation Pathway

Popis výsledku anglicky

It has been proposed that the fullerene formation mechanism involves either a top-down or bottom up pathway. Despite different starting points, both mechanisms approve that particular fullerenes or metallofullerenes are formed through a consecutive stepwise process involving Stone-Wales transformations (SWTs) and C-2 losses or additions. However, the formation pathway has seldomly been defined at the atomic level due to the missing-link fullerenes. Herein, we present the isolation and crystallographic characterization of two isomeric clusterfullerenes Sc2O@C-2v(3)-C-78 and Sc2O@D-3h(5)-C-78, which are closely related via a single-step Stone Wales (SW) transformation. More importantly, these novel Sc2O@C-78 isomers represent the key links in a well-defined formation pathway for the majority of solvent-extractable clusterfullerenes Sc2O@C-2n (n = 38-41), providing molecular structural evidence for the less confirmed fullerene formation mechanism. Furthermore, DFT calculations reveal a SWT with a notably low activation barrier for these Sc2O@C-78 isomers, which may rationalize the established fullerene formation pathway. Additional characterizations demonstrate that these Sc2O@C-78 isomers feature different energy bandgaps and electrochemical behaviors, indicating the impact of SW defects on the energetic and electrochemical characteristics of metallofullerenes.

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

<a href="/cs/project/GAP208%2F10%2F1724" target="_blank" >GAP208/10/1724: Studium struktury a dynamiky povrchu ledu za přítomnosti příměsí a atmosférických polutantů pomocí molekulových simulací</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2016

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

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Svazek periodika

55

Číslo periodika v rámci svazku

21

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

8

Strana od-do

11354-11361

Kód UT WoS článku

000387428200060

EID výsledku v databázi Scopus

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