Supramolecular Covalence in Bifurcated Chalcogen Bonding

J 2017

Supramolecular Covalence in Bifurcated Chalcogen Bonding

BORA, Pankaj Lochan, Martin NOVÁK, Jan NOVOTNÝ, Cina FOROUTANNEJAD, Radek MAREK et. al.

Basic information

Original name

Supramolecular Covalence in Bifurcated Chalcogen Bonding

Authors

BORA, Pankaj Lochan (356 India, belonging to the institution), Martin NOVÁK (203 Czech Republic, belonging to the institution), Jan NOVOTNÝ (203 Czech Republic, belonging to the institution), Cina FOROUTANNEJAD (364 Islamic Republic of Iran, belonging to the institution) and Radek MAREK (203 Czech Republic, guarantor, belonging to the institution)

Edition

Chemistry - A European Journal, Weinheim, Wiley, 2017, 0947-6539

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10403 Physical chemistry

Country of publisher

Germany

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

DOI: 10.1002/chem.201700179

Impact factor

Impact factor: 5.160

RIV identification code

RIV/00216224:14740/17:00096314

Organization unit

Central European Institute of Technology

DOI

http://dx.doi.org/10.1002/chem.201700179

UT WoS

000402640600024

Keywords in English

chalcogen bond;supramolecule;covalence;NBO;molecular orbitals;interacting quantum atoms;QTAIM

Abstract

V originále

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.

Links

LQ1601, research and development project

Name: CEITEC 2020 (Acronym: CEITEC2020)

Investor: Ministry of Education, Youth and Sports of the CR

Files attached

CEJ17_23_7315.pdf

Request the author's version of the file

Citovat

BORA, Pankaj Lochan, Martin NOVÁK, Jan NOVOTNÝ, Cina FOROUTANNEJAD and Radek MAREK. Supramolecular Covalence in Bifurcated Chalcogen Bonding. Chemistry - A European Journal. Weinheim: Wiley, 2017, vol. 23, No 30, p. 7315-7323. ISSN 0947-6539. Available from: https://dx.doi.org/10.1002/chem.201700179.

@article{1375788,
   author = {Bora, Pankaj Lochan and Novák, Martin and Novotný, Jan and Foroutannejad, Cina and Marek, Radek},
   article_location = {Weinheim},
   article_number = {30},
   doi = {http://dx.doi.org/10.1002/chem.201700179},
   keywords = {chalcogen bond;supramolecule;covalence;NBO;molecular orbitals;interacting quantum atoms;QTAIM},
   language = {eng},
   issn = {0947-6539},
   journal = {Chemistry - A European Journal},
   title = {Supramolecular Covalence in Bifurcated Chalcogen Bonding},
   url = {http://dx.doi.org/10.1002/chem.201700179},
   volume = {23},
   year = {2017}
}

TY  - JOUR
ID  - 1375788
AU  - Bora, Pankaj Lochan - Novák, Martin - Novotný, Jan - Foroutannejad, Cina - Marek, Radek
PY  - 2017
TI  - Supramolecular Covalence in Bifurcated Chalcogen Bonding
JF  - Chemistry - A European Journal
VL  - 23
IS  - 30
SP  - 7315-7323
EP  - 7315-7323
PB  - Wiley
SN  - 09476539
KW  - chalcogen bond;supramolecule;covalence;NBO;molecular orbitals;interacting quantum atoms;QTAIM
UR  - http://dx.doi.org/10.1002/chem.201700179
L2  - http://dx.doi.org/10.1002/chem.201700179
N2  - 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.
ER  -

BORA, Pankaj Lochan, Martin NOVÁK, Jan NOVOTNÝ, Cina FOROUTANNEJAD and Radek MAREK. Supramolecular Covalence in Bifurcated Chalcogen Bonding. \textit{Chemistry - A European Journal}. Weinheim: Wiley, 2017, vol.~23, No~30, p.~7315-7323. ISSN~0947-6539. Available from: https://dx.doi.org/10.1002/chem.201700179.

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