The pnictogen bond: a quantitative molecular orbital picture

L. de Azevedo Santos; T.A. Hamlin; T.C. Ramalho; F.M. Bickelhaupt

doi:10.1039/d1cp01571k

The pnictogen bond: a quantitative molecular orbital picture

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Abstract

We have analyzed the structure and stability of archetypal pnictogen-bonded model complexes D3Pn⋯A−(Pn = N, P, As, Sb; D, A = F, Cl, Br) using state-of-the-art relativistic density functional calculations at the ZORA-M06/QZ4P level. We have accomplished two tasks: (i) to compute accurate trends in pnictogen-bond strength based on a set of consistent data; and (ii) to rationalize these trends in terms of detailed analyses of the bonding mechanism based on quantitative Kohn-Sham molecular orbital (KS-MO) theory in combination with a canonical energy decomposition analysis (EDA) and Voronoi deformation density (VDD) analyses of the charge distribution. We have found that pnictogen bonds have a significant covalent character stemming from strong HOMO-LUMO interactions between the lone pair of A−and σ* of D3Pn. As such, the underlying mechanism of the pnictogen bond is similar to that of hydrogen, halogen, and chalcogen bonds.

Original language	English
Pages (from-to)	13842-13852
Number of pages	11
Journal	Physical Chemistry Chemical Physics
Volume	23
Issue number	25
Early online date	4 Jun 2021
DOIs	https://doi.org/10.1039/d1cp01571k
Publication status	Published - 7 Jul 2021

Bibliographical note

Funding

We thank the Brazilian agencies Fundação de Amparo àPesquisa do Estado de Minas Gerais (FAPEMIG) and Coordenação de Aperfeiçoamento de Pessoal de Ńıvel Superior (CAPES) for the scholarship to LAS, Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) for the fellowship to TCR, and the Netherlands Organization for Scientific Research (NWO) for all the support. This work was carried out on the Dutch national e-infrastructure with the support of SURF Cooperative. We thank the Brazilian agencies Funda??o de Amparo ? Pesquisa do Estado de Minas Gerais (FAPEMIG) and Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) for the scholarship to LAS, Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) for the fellowship to TCR, and the Netherlands Organization for Scientific Research (NWO) for all the support. This work was carried out on the Dutch national e-infrastructure with the support of SURF Cooperative.

Funders
Aperfei?oamento de Pessoal de N?vel Superior
Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico
Fundação de Amparo àPesquisa do Estado de Minas Gerais
Pesquisa do Estado de Minas Gerais
SURF Cooperative
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Conselho Nacional de Desenvolvimento Científico e Tecnológico
Fundação de Amparo à Pesquisa do Estado de Minas Gerais

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

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title = "The pnictogen bond: a quantitative molecular orbital picture",

abstract = "We have analyzed the structure and stability of archetypal pnictogen-bonded model complexes D3Pn⋯A−(Pn = N, P, As, Sb; D, A = F, Cl, Br) using state-of-the-art relativistic density functional calculations at the ZORA-M06/QZ4P level. We have accomplished two tasks: (i) to compute accurate trends in pnictogen-bond strength based on a set of consistent data; and (ii) to rationalize these trends in terms of detailed analyses of the bonding mechanism based on quantitative Kohn-Sham molecular orbital (KS-MO) theory in combination with a canonical energy decomposition analysis (EDA) and Voronoi deformation density (VDD) analyses of the charge distribution. We have found that pnictogen bonds have a significant covalent character stemming from strong HOMO-LUMO interactions between the lone pair of A−and σ* of D3Pn. As such, the underlying mechanism of the pnictogen bond is similar to that of hydrogen, halogen, and chalcogen bonds.",

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AU - de Azevedo Santos, L.

AU - Hamlin, T.A.

AU - Ramalho, T.C.

AU - Bickelhaupt, F.M.

PY - 2021/7/7

Y1 - 2021/7/7

N2 - We have analyzed the structure and stability of archetypal pnictogen-bonded model complexes D3Pn⋯A−(Pn = N, P, As, Sb; D, A = F, Cl, Br) using state-of-the-art relativistic density functional calculations at the ZORA-M06/QZ4P level. We have accomplished two tasks: (i) to compute accurate trends in pnictogen-bond strength based on a set of consistent data; and (ii) to rationalize these trends in terms of detailed analyses of the bonding mechanism based on quantitative Kohn-Sham molecular orbital (KS-MO) theory in combination with a canonical energy decomposition analysis (EDA) and Voronoi deformation density (VDD) analyses of the charge distribution. We have found that pnictogen bonds have a significant covalent character stemming from strong HOMO-LUMO interactions between the lone pair of A−and σ* of D3Pn. As such, the underlying mechanism of the pnictogen bond is similar to that of hydrogen, halogen, and chalcogen bonds.

AB - We have analyzed the structure and stability of archetypal pnictogen-bonded model complexes D3Pn⋯A−(Pn = N, P, As, Sb; D, A = F, Cl, Br) using state-of-the-art relativistic density functional calculations at the ZORA-M06/QZ4P level. We have accomplished two tasks: (i) to compute accurate trends in pnictogen-bond strength based on a set of consistent data; and (ii) to rationalize these trends in terms of detailed analyses of the bonding mechanism based on quantitative Kohn-Sham molecular orbital (KS-MO) theory in combination with a canonical energy decomposition analysis (EDA) and Voronoi deformation density (VDD) analyses of the charge distribution. We have found that pnictogen bonds have a significant covalent character stemming from strong HOMO-LUMO interactions between the lone pair of A−and σ* of D3Pn. As such, the underlying mechanism of the pnictogen bond is similar to that of hydrogen, halogen, and chalcogen bonds.

U2 - 10.1039/d1cp01571k

DO - 10.1039/d1cp01571k

M3 - Article

SN - 1463-9076

VL - 23

SP - 13842

EP - 13852

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 25

ER -

The pnictogen bond: a quantitative molecular orbital picture

Abstract

Bibliographical note

Funding

UN SDGs

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