Supramolecular Covalence in Bifurcated Chalcogen Bonding

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14740%2F17%3A00096314" target="_blank" >RIV/00216224:14740/17:00096314 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1002/chem.201700179" target="_blank" >http://dx.doi.org/10.1002/chem.201700179</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.201700179" target="_blank" >10.1002/chem.201700179</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Supramolecular Covalence in Bifurcated Chalcogen Bonding

Popis výsledku v původním jazyce

Supramolecular interactions are generally classified as noncovalent. However, recent studies have demonstrated that many of these interactions are stabilized by a significant covalent component. Herein, for systems of the general structure [MX6]2-:YX2 (M=Se or Pt; Y=S, Se, or Te; X=F, Cl, Br, I), featuring bifurcated chalcogen bonding, it is shown that, although electrostatic parameters are useful for estimating the long-range electrostatic component of the interaction, they fail to predict the correct order of binding energies in a series of compounds. Instead, the Lewis basicity of the individual substituents X on the chalcogen atom governs the trends in the binding energies through fine-tuning the covalent character of the chalcogen bond. The effects of substituents on the binding energy and supramolecular electron sharing are consistently identified by an arsenal of theoretical methods, ranging from approaches based on the quantum chemical topology to analytical tools based on the localized molecular orbitals. The chalcogen bonding investigated herein is driven by orbital interactions with significant electron sharing; this can be designated as supramolecular covalence.

Název v anglickém jazyce

Supramolecular Covalence in Bifurcated Chalcogen Bonding

Popis výsledku anglicky

Supramolecular interactions are generally classified as noncovalent. However, recent studies have demonstrated that many of these interactions are stabilized by a significant covalent component. Herein, for systems of the general structure [MX6]2-:YX2 (M=Se or Pt; Y=S, Se, or Te; X=F, Cl, Br, I), featuring bifurcated chalcogen bonding, it is shown that, although electrostatic parameters are useful for estimating the long-range electrostatic component of the interaction, they fail to predict the correct order of binding energies in a series of compounds. Instead, the Lewis basicity of the individual substituents X on the chalcogen atom governs the trends in the binding energies through fine-tuning the covalent character of the chalcogen bond. The effects of substituents on the binding energy and supramolecular electron sharing are consistently identified by an arsenal of theoretical methods, ranging from approaches based on the quantum chemical topology to analytical tools based on the localized molecular orbitals. The chalcogen bonding investigated herein is driven by orbital interactions with significant electron sharing; this can be designated as supramolecular covalence.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/LQ1601" target="_blank" >LQ1601: CEITEC 2020</a><br>

Návaznosti

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

Rok uplatnění

2017

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

23

Číslo periodika v rámci svazku

30

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

9

Strana od-do

7315-7323

Kód UT WoS článku

000402640600024

EID výsledku v databázi Scopus

2-s2.0-85018677081