Azine Steric Hindrances Switch Halogen Bonding to N-Arylation upon Interplay with σ-Hole Donating Haloarenenitriles

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Azine Steric Hindrances Switch Halogen Bonding to N-Arylation upon Interplay with σ-Hole Donating Haloarenenitriles. / Baykov, Sergey V.; Geyl, Kirill K.; Ivanov, Daniil M.; Gomila, Rosa M.; Frontera, Antonio; Kukushkin, Vadim Y.

In: Chemistry - An Asian Journal, Vol. 16, No. 11, 01.06.2021, p. 1445-1455.

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

BibTeX

@article{c55288552ab5477d8cd4951ff28796d6,

title = "Azine Steric Hindrances Switch Halogen Bonding to N-Arylation upon Interplay with σ-Hole Donating Haloarenenitriles",

abstract = "An interplay between 4-bromo- and 4-iodo-5-nitrophthalonitriles (XNPN, X=Br or I) and any one of the azines (pyridine 1, 4-dimethylaminopyridine 2, isoquinoline 3, 4-cyanopyridine 4, 2-methylpyridine 5, 2-aminopyridine 6, quinoline 7, 1-methylisoquinoline 8, and 2,2{\textquoteright}-bipyridine 9) proceeds differently depending on steric and electronic effects of the heterocycles. Sterically unhindered azines 1–3 underwent N-arylation to give the corresponding azinium salts (characterized by 1H and 13C{H} NMR and high-resolution ESI-MS). In contrast, azines 4–9 with sterically hindered N atoms or bearing an electron-withdrawing substituent, form stable co-crystals with XNPN, where two interacting molecules are bound by halogen bonding. In all obtained co-crystals, X⋅⋅⋅N structure-directed halogen bonds were recognized and theoretically evaluated including DFT calculations (PBE0-D3/def2-TZVP level of theory), QTAIM analysis, molecular electrostatic potential surfaces, and noncovalent interaction plot index. Estimated energies of halogen bonding vary from −7.6 kcal/mol (for 6 ⋅ INPN) to −11.4 kcal/mol (5 ⋅ INPN).",

keywords = "azines, halogen bonding, nitriles, noncovalent interactions, self-assembly",

author = "Baykov, {Sergey V.} and Geyl, {Kirill K.} and Ivanov, {Daniil M.} and Gomila, {Rosa M.} and Antonio Frontera and Kukushkin, {Vadim Y.}",

note = "Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",

year = "2021",

month = jun,

day = "1",

doi = "10.1002/asia.202100282",

language = "English",

volume = "16",

pages = "1445--1455",

journal = "Chemistry - An Asian Journal",

issn = "1861-4728",

publisher = "Wiley-Blackwell",

number = "11",

}

RIS

TY - JOUR

T1 - Azine Steric Hindrances Switch Halogen Bonding to N-Arylation upon Interplay with σ-Hole Donating Haloarenenitriles

AU - Baykov, Sergey V.

AU - Geyl, Kirill K.

AU - Ivanov, Daniil M.

AU - Gomila, Rosa M.

AU - Frontera, Antonio

AU - Kukushkin, Vadim Y.

PY - 2021/6/1

Y1 - 2021/6/1

N2 - An interplay between 4-bromo- and 4-iodo-5-nitrophthalonitriles (XNPN, X=Br or I) and any one of the azines (pyridine 1, 4-dimethylaminopyridine 2, isoquinoline 3, 4-cyanopyridine 4, 2-methylpyridine 5, 2-aminopyridine 6, quinoline 7, 1-methylisoquinoline 8, and 2,2’-bipyridine 9) proceeds differently depending on steric and electronic effects of the heterocycles. Sterically unhindered azines 1–3 underwent N-arylation to give the corresponding azinium salts (characterized by 1H and 13C{H} NMR and high-resolution ESI-MS). In contrast, azines 4–9 with sterically hindered N atoms or bearing an electron-withdrawing substituent, form stable co-crystals with XNPN, where two interacting molecules are bound by halogen bonding. In all obtained co-crystals, X⋅⋅⋅N structure-directed halogen bonds were recognized and theoretically evaluated including DFT calculations (PBE0-D3/def2-TZVP level of theory), QTAIM analysis, molecular electrostatic potential surfaces, and noncovalent interaction plot index. Estimated energies of halogen bonding vary from −7.6 kcal/mol (for 6 ⋅ INPN) to −11.4 kcal/mol (5 ⋅ INPN).

AB - An interplay between 4-bromo- and 4-iodo-5-nitrophthalonitriles (XNPN, X=Br or I) and any one of the azines (pyridine 1, 4-dimethylaminopyridine 2, isoquinoline 3, 4-cyanopyridine 4, 2-methylpyridine 5, 2-aminopyridine 6, quinoline 7, 1-methylisoquinoline 8, and 2,2’-bipyridine 9) proceeds differently depending on steric and electronic effects of the heterocycles. Sterically unhindered azines 1–3 underwent N-arylation to give the corresponding azinium salts (characterized by 1H and 13C{H} NMR and high-resolution ESI-MS). In contrast, azines 4–9 with sterically hindered N atoms or bearing an electron-withdrawing substituent, form stable co-crystals with XNPN, where two interacting molecules are bound by halogen bonding. In all obtained co-crystals, X⋅⋅⋅N structure-directed halogen bonds were recognized and theoretically evaluated including DFT calculations (PBE0-D3/def2-TZVP level of theory), QTAIM analysis, molecular electrostatic potential surfaces, and noncovalent interaction plot index. Estimated energies of halogen bonding vary from −7.6 kcal/mol (for 6 ⋅ INPN) to −11.4 kcal/mol (5 ⋅ INPN).

KW - azines

KW - halogen bonding

KW - nitriles

KW - noncovalent interactions

KW - self-assembly

UR - http://www.scopus.com/inward/record.url?scp=85105173184&partnerID=8YFLogxK

U2 - 10.1002/asia.202100282

DO - 10.1002/asia.202100282

M3 - Article

C2 - 33844884

AN - SCOPUS:85105173184

VL - 16

SP - 1445

EP - 1455

JO - Chemistry - An Asian Journal

JF - Chemistry - An Asian Journal

SN - 1861-4728

IS - 11

ER -

ID: 77311000