Multi-Center Covalency: Revisiting the Nature of Anion-pi
Interactions

J 2015

Multi-Center Covalency: Revisiting the Nature of Anion-pi Interactions

FOROUTANNEJAD, Cina; Zahra BADRI a Radek MAREK

Základní údaje

Originální název

Multi-Center Covalency: Revisiting the Nature of Anion-pi Interactions

Autoři

FOROUTANNEJAD, Cina; Zahra BADRI a Radek MAREK

Vydání

Physical Chemistry Chemical Physics, CAMBRIDGE, Royal Society of Chemistry, 2015, 1463-9076

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10403 Physical chemistry

Stát vydavatele

Velká Británie a Severní Irsko

Utajení

není předmětem státního či obchodního tajemství

Odkazy

DOI: 10.1039/C5CP05777A

Impakt faktor

Impact factor: 4.449

Kód RIV

RIV/00216224:14740/15:00084446

Organizační jednotka

Středoevropský technologický institut

DOI

https://doi.org/10.1039/C5CP05777A

UT WoS

000364862000050

EID Scopus

2-s2.0-84946925411

Klíčová slova anglicky

anion-pi; bonding; interacting quantum atoms; covalency; exchange-correlation

Štítky

rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 1. 4. 2016 12:32, Mgr. Eva Špillingová

Anotace

V originále

Exploring the nature of anion–pi bonding by means of the Quantum Theory of Atoms in Molecules (QTAIM) and an energy decomposition scheme on the basis of Interacting Quantum Atoms (IQA) theory led us to conclude that these non-classical interactions benefit from “multi-center covalency” far more than from the electrostatics. Comparing anion–pi systems to closely related covalent anion–sigma complexes reveals that the anion–pi systems benefit from an extensive degree of electron sharing between the anions and all atoms of the pi-rings. Besides, decomposition of the binding energy into classical (electrostatics) and non-classical (exchange–correlation) components demonstrates that in contrast to previous reports, the anion–pi complexes are local minima, if and only if the non-classical contribution to binding energy surpasses that of the electrostatics. This suggests that the stable anion–pi complexes with the anions atop the pi-rings might be prepared with pi-systems that benefit more from the exchange–correlation term, such as extended pi-systems, but not with strong electrostatic pi-receptors. This conclusion is in line with the tendency of strong pi-acids to form the sigma-complexes with more covalent character instead of the pi-complexes.

Návaznosti

ED1.1.00/02.0068, projekt VaV

Název: CEITEC - central european institute of technology

4SGA8546, interní kód MU

Název: Towards the graphene selective receptors: the role of electric field in non-covalent interactions (Akronym: GrapheneReceptor)

Investor: Jihomoravský kraj, Towards the graphene selective receptors: the role of electric field in non-covalent interactions, Granty pro zahraniční vědce

Přiložené soubory

PCCP15_17_30670.pdf

Požádat o autorskou verzi souboru

Citovat

FOROUTANNEJAD, Cina; Zahra BADRI a Radek MAREK. Multi-Center Covalency: Revisiting the Nature of Anion-pi Interactions. Physical Chemistry Chemical Physics. CAMBRIDGE: Royal Society of Chemistry, 2015, roč. 17, č. 45, s. 30670-30679. ISSN 1463-9076. Dostupné z: https://doi.org/10.1039/C5CP05777A.

@article{1315462,
   author = {Foroutannejad, Cina and Badri, Zahra and Marek, Radek},
   article_location = {CAMBRIDGE},
   article_number = {45},
   doi = {https://doi.org/10.1039/C5CP05777A},
   keywords = {anion-pi; bonding; interacting quantum atoms; covalency; exchange-correlation},
   language = {eng},
   issn = {1463-9076},
   journal = {Physical Chemistry Chemical Physics},
   title = {Multi-Center Covalency: Revisiting the Nature of Anion-pi Interactions},
   url = {http://dx.doi.org/10.1039/C5CP05777A},
   volume = {17},
   year = {2015}
}

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JF  - Physical Chemistry Chemical Physics
VL  - 17
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SP  - 30670-30679
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PB  - Royal Society of Chemistry
SN  - 14639076
KW  - anion-pi
KW  - bonding
KW  - interacting quantum atoms
KW  - covalency
KW  - exchange-correlation
UR  - http://dx.doi.org/10.1039/C5CP05777A
L2  - http://dx.doi.org/10.1039/C5CP05777A
N2  - Exploring the nature of anion–pi bonding by means of the Quantum Theory of Atoms in Molecules (QTAIM) and an energy decomposition scheme on the basis of Interacting Quantum Atoms (IQA) theory led us to conclude that these non-classical interactions benefit from “multi-center covalency” far more than from the electrostatics. Comparing anion–pi systems to closely related covalent anion–sigma complexes reveals that the anion–pi systems benefit from an extensive degree of electron sharing between the anions and all atoms of the pi-rings. Besides, decomposition of the binding energy into classical (electrostatics) and non-classical (exchange–correlation) components demonstrates that in contrast to previous reports, the anion–pi complexes are local minima, if and only if the non-classical contribution to binding energy surpasses that of the electrostatics. This suggests that the stable anion–pi complexes with the anions atop the pi-rings might be prepared with pi-systems that benefit more from the exchange–correlation term, such as extended pi-systems, but not with strong electrostatic pi-receptors. This conclusion is in line with the tendency of strong pi-acids to form the sigma-complexes with more covalent character instead of the pi-complexes.
ER  -

FOROUTANNEJAD, Cina; Zahra BADRI a Radek MAREK. Multi-Center Covalency: Revisiting the Nature of Anion-pi Interactions. \textit{Physical Chemistry Chemical Physics}. CAMBRIDGE: Royal Society of Chemistry, 2015, roč.~17, č.~45, s.~30670-30679. ISSN~1463-9076. Dostupné z: https://doi.org/10.1039/C5CP05777A.

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