The essential role of symmetry in understanding 3He chemical shifts in endohedral helium fullerenes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F23%3A00571079" target="_blank" >RIV/61388963:_____/23:00571079 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/70883521:28610/23:63567138

Výsledek na webu

<a href="https://doi.org/10.1039/D3CP00256J" target="_blank" >https://doi.org/10.1039/D3CP00256J</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d3cp00256j" target="_blank" >10.1039/d3cp00256j</a>

Jazyk výsledku

angličtina

Název v původním jazyce

The essential role of symmetry in understanding 3He chemical shifts in endohedral helium fullerenes

Popis výsledku v původním jazyce

The 3He atom is an excellent NMR probe, particularly when enclosed in endohedral helium fullerenes. The 3He chemical shift, δ(3He), in fullerenes spans a range from ca. −50 to +10 ppm, and changes sensitively between different cages, isomers, and external substituents. Reduction of the fullerenes to anions changes the δ(3He) dramatically and unexpectedly, particularly for the most symmetric and also the most abundant C60 and C70 cages. While the 3He atom is shielded by ∼43 ppm upon charging the He@C60 to He@C606−, it is correspondingly deshielded by ∼37 ppm in the He@C70/He@C706− pair. Here, we show that such puzzling differences in δ(3He) relate to the high symmetry of the host fullerene cages. While similar shielding is induced at the 3He atom by the core orbitals of different cages, the symmetry of the cage allows or quenches large paramagnetic, i.e., deshielding orbital interactions of frontier orbitals upon charging of the cage, which is directly responsible for the large observed chemical shift range of endohedral 3He.

Název v anglickém jazyce

The essential role of symmetry in understanding 3He chemical shifts in endohedral helium fullerenes

Popis výsledku anglicky

The 3He atom is an excellent NMR probe, particularly when enclosed in endohedral helium fullerenes. The 3He chemical shift, δ(3He), in fullerenes spans a range from ca. −50 to +10 ppm, and changes sensitively between different cages, isomers, and external substituents. Reduction of the fullerenes to anions changes the δ(3He) dramatically and unexpectedly, particularly for the most symmetric and also the most abundant C60 and C70 cages. While the 3He atom is shielded by ∼43 ppm upon charging the He@C60 to He@C606−, it is correspondingly deshielded by ∼37 ppm in the He@C70/He@C706− pair. Here, we show that such puzzling differences in δ(3He) relate to the high symmetry of the host fullerene cages. While similar shielding is induced at the 3He atom by the core orbitals of different cages, the symmetry of the cage allows or quenches large paramagnetic, i.e., deshielding orbital interactions of frontier orbitals upon charging of the cage, which is directly responsible for the large observed chemical shift range of endohedral 3He.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA21-17806S" target="_blank" >GA21-17806S: Endohedrální fullereny pro molekulární součástky: Memristory a spinristory</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

1463-9084

Svazek periodika

25

Číslo periodika v rámci svazku

15

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

8

Strana od-do

10620-10627

Kód UT WoS článku

000961024700001

EID výsledku v databázi Scopus

2-s2.0-85152102713