Stacking interactions: a supramolecular approach to upgrade weak halogen bond donors

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Stacking interactions: a supramolecular approach to upgrade weak halogen bond donors. / Байков, Сергей Валентинович ; Иванов, Даниил Михайлович; Kasatkina, S. O.; Galmés, Bartomeu; Frontera, Antonio; Resnati, Giuseppe; Кукушкин, Вадим Юрьевич.

In: Chemistry - A European Journal, Vol. 28, No. 70, e202201869, 15.12.2022.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{bedec465bfdb4b75b1a0998a1a2b97e7,

title = "Stacking interactions: a supramolecular approach to upgrade weak halogen bond donors",

abstract = "The co‐crystallization of tetracyanobenzene (TCB) with haloarenes ArX provided six new co‐crystals TCB•ArX (ArX = PhCl, PhBr, 4‐MeC 6 H 4 Cl, 4‐MeC 6 H 4 Br, 4‐MeOC 6 H 4 Cl, 1,2‐Br 2 C 6 H 4 ) which were studied by X‐ray diffraction. In these systems, the strong collective effect of π⋯π stacking interactions and lone pair‐(X)⋯π‐hole‐(C) bondings between TCB and ArX promote the strength of X⋯N cyano halogen bonding (HaB). Theoretical studies showed that the stacking interactions affect the σ‐hole depth of the haloarenes, thus significantly boosting their ability to function as HaB donors. According to the molecular electrostatic potential calculations, the σ‐ hole‐(Cl) value (1.5 kcal/mol) in the haloarene 4‐MeOC 6 H 4 Cl (featuring an electron‐rich arene moiety and exhibiting very poor σ‐hole‐(Cl) ability) increases significantly in the stacked trimer (TCB) 2 •4‐MeOC 6 H 4 Cl (12.5 kcal/mol). Theoretical DFT calculations demonstrate the dramatic increase of X⋯N cyano HaB strength for stacked trimers in comparison with parent unstacked haloarenes.",

keywords = "DFT calculations, crystal engineering, halogen bonding, noncovalent interactions, staking",

author = "Байков, {Сергей Валентинович} and Иванов, {Даниил Михайлович} and Kasatkina, {S. O.} and Bartomeu Galm{\'e}s and Antonio Frontera and Giuseppe Resnati and Кукушкин, {Вадим Юрьевич}",

note = "Publisher Copyright: {\textcopyright} 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.",

year = "2022",

month = dec,

day = "15",

doi = "10.1002/chem.202201869",

language = "English",

volume = "28",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-Blackwell",

number = "70",

}

RIS

TY - JOUR

T1 - Stacking interactions: a supramolecular approach to upgrade weak halogen bond donors

AU - Байков, Сергей Валентинович

AU - Иванов, Даниил Михайлович

AU - Kasatkina, S. O.

AU - Galmés, Bartomeu

AU - Frontera, Antonio

AU - Resnati, Giuseppe

AU - Кукушкин, Вадим Юрьевич

PY - 2022/12/15

Y1 - 2022/12/15

N2 - The co‐crystallization of tetracyanobenzene (TCB) with haloarenes ArX provided six new co‐crystals TCB•ArX (ArX = PhCl, PhBr, 4‐MeC 6 H 4 Cl, 4‐MeC 6 H 4 Br, 4‐MeOC 6 H 4 Cl, 1,2‐Br 2 C 6 H 4 ) which were studied by X‐ray diffraction. In these systems, the strong collective effect of π⋯π stacking interactions and lone pair‐(X)⋯π‐hole‐(C) bondings between TCB and ArX promote the strength of X⋯N cyano halogen bonding (HaB). Theoretical studies showed that the stacking interactions affect the σ‐hole depth of the haloarenes, thus significantly boosting their ability to function as HaB donors. According to the molecular electrostatic potential calculations, the σ‐ hole‐(Cl) value (1.5 kcal/mol) in the haloarene 4‐MeOC 6 H 4 Cl (featuring an electron‐rich arene moiety and exhibiting very poor σ‐hole‐(Cl) ability) increases significantly in the stacked trimer (TCB) 2 •4‐MeOC 6 H 4 Cl (12.5 kcal/mol). Theoretical DFT calculations demonstrate the dramatic increase of X⋯N cyano HaB strength for stacked trimers in comparison with parent unstacked haloarenes.

AB - The co‐crystallization of tetracyanobenzene (TCB) with haloarenes ArX provided six new co‐crystals TCB•ArX (ArX = PhCl, PhBr, 4‐MeC 6 H 4 Cl, 4‐MeC 6 H 4 Br, 4‐MeOC 6 H 4 Cl, 1,2‐Br 2 C 6 H 4 ) which were studied by X‐ray diffraction. In these systems, the strong collective effect of π⋯π stacking interactions and lone pair‐(X)⋯π‐hole‐(C) bondings between TCB and ArX promote the strength of X⋯N cyano halogen bonding (HaB). Theoretical studies showed that the stacking interactions affect the σ‐hole depth of the haloarenes, thus significantly boosting their ability to function as HaB donors. According to the molecular electrostatic potential calculations, the σ‐ hole‐(Cl) value (1.5 kcal/mol) in the haloarene 4‐MeOC 6 H 4 Cl (featuring an electron‐rich arene moiety and exhibiting very poor σ‐hole‐(Cl) ability) increases significantly in the stacked trimer (TCB) 2 •4‐MeOC 6 H 4 Cl (12.5 kcal/mol). Theoretical DFT calculations demonstrate the dramatic increase of X⋯N cyano HaB strength for stacked trimers in comparison with parent unstacked haloarenes.

KW - DFT calculations

KW - crystal engineering

KW - halogen bonding

KW - noncovalent interactions

KW - staking

UR - https://www.mendeley.com/catalogue/e568e6ea-bd54-35ea-843d-5ab287e7b4f9/

UR - http://www.scopus.com/inward/record.url?scp=85141763741&partnerID=8YFLogxK

U2 - 10.1002/chem.202201869

DO - 10.1002/chem.202201869

M3 - Article

VL - 28

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 70

M1 - e202201869

ER -

ID: 100022958