How Does a Container Affect Acidity of its Content? Charge-Depletion Bonding Inside Fullerenes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14740%2F18%3A00100826" target="_blank" >RIV/00216224:14740/18:00100826 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388963:_____/18:00489832

Výsledek na webu

<a href="http://dx.doi.org/10.1002/chem.201706017" target="_blank" >http://dx.doi.org/10.1002/chem.201706017</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.201706017" target="_blank" >10.1002/chem.201706017</a>

Jazyk výsledku

angličtina

Název v původním jazyce

How Does a Container Affect Acidity of its Content? Charge-Depletion Bonding Inside Fullerenes

Popis výsledku v původním jazyce

A recent study (Sci. Adv. 2017, 3, e1602833) has shown that FH...OH2 hydrogen bond in a HF·H2O pair substantially shortens and the H-F bond elongates upon encapsulation of the cluster in C70 fullerene. This has been attributed to compression of the HF·H2O pair inside the cavity of C70. Here we present theoretical evidence that the effect is not caused by a mere compression of the H2O·HF pair but it is related to a strong lone-pair-pi (LP-pi) bonding with the fullerene cage. To support this argument, a systematic electronic structure study of selected small molecules (HF, H2O, and NH3) and their pairs enclosed in fullerene cages (C60, C70, and C90) has been performed. Bonding analysis revealed unique LP-picage interactions with a charge-depletion character in the bonding region, unlike usual LP-pi bonds. The LP-picage interactions were found to be responsible for elongation of the H-F bond. Thus, the HF appears to be more acidic inside the cage. The shortening of the FH…OH2 contact in (HF·H2O)@C70 originates from an increased acidity of the HF inside the fullerenes. Such trends are also observed in other studied systems.

Název v anglickém jazyce

How Does a Container Affect Acidity of its Content? Charge-Depletion Bonding Inside Fullerenes

Popis výsledku anglicky

A recent study (Sci. Adv. 2017, 3, e1602833) has shown that FH...OH2 hydrogen bond in a HF·H2O pair substantially shortens and the H-F bond elongates upon encapsulation of the cluster in C70 fullerene. This has been attributed to compression of the HF·H2O pair inside the cavity of C70. Here we present theoretical evidence that the effect is not caused by a mere compression of the H2O·HF pair but it is related to a strong lone-pair-pi (LP-pi) bonding with the fullerene cage. To support this argument, a systematic electronic structure study of selected small molecules (HF, H2O, and NH3) and their pairs enclosed in fullerene cages (C60, C70, and C90) has been performed. Bonding analysis revealed unique LP-picage interactions with a charge-depletion character in the bonding region, unlike usual LP-pi bonds. The LP-picage interactions were found to be responsible for elongation of the H-F bond. Thus, the HF appears to be more acidic inside the cage. The shortening of the FH…OH2 contact in (HF·H2O)@C70 originates from an increased acidity of the HF inside the fullerenes. Such trends are also observed in other studied systems.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

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

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

1521-3765

Svazek periodika

24

Číslo periodika v rámci svazku

17

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

5

Strana od-do

4245-4249

Kód UT WoS článku

000428376900008

EID výsledku v databázi Scopus

2-s2.0-85042620565