Research output: Contribution to journal › Article › peer-review
Diaryliodonium Tetracyanidometallates Self-Assemble into Halogen-Bonded Square-Like Arrays. / Suslonov, Vitalii V.; Soldatova, Natalia S.; Postnikov, Pavel S.; Resnati, Giuseppe; Kukushkin, Vadim Yu; Ivanov, Daniil M.; Bokach, Nadezhda A.
In: Crystal Growth and Design, Vol. 22, No. 4, 25.03.2022, p. 2749-2758.Research output: Contribution to journal › Article › peer-review
}
TY - JOUR
T1 - Diaryliodonium Tetracyanidometallates Self-Assemble into Halogen-Bonded Square-Like Arrays
AU - Suslonov, Vitalii V.
AU - Soldatova, Natalia S.
AU - Postnikov, Pavel S.
AU - Resnati, Giuseppe
AU - Kukushkin, Vadim Yu
AU - Ivanov, Daniil M.
AU - Bokach, Nadezhda A.
N1 - Publisher Copyright: © 2022 American Chemical Society. All rights reserved.
PY - 2022/3/25
Y1 - 2022/3/25
N2 - Two diphenyliodonium tetracyanidometallates, [Ph2I]2[M(CN)4] (M = Ni and Pd), were prepared through anion metathesis. Their X-ray structural analyses show that the structure-defining contact for both crystals is the charge-assisted I···N halogen bond (HaB) formed between the I atom of the iodonium cations and the N atoms of the CN-ligands. These HaBs assemble the bidentate and 90°-orienting HaB donor Ph2I+and the tetradentate, square planar, and 90/180°-orienting HaB acceptors [M(CN)4]2-into supramolecular rectangles, which further assemble into infinite chains by sharing the vertexes occupied by the [M(CN)4]2-anions. The noncovalent nature of these contacts was confirmed by density functional theory calculations (M06/def2-TZVP) followed by combined topological analysis of the electron density distribution in the quantum theory of the atoms-in-molecules approach and noncovalent interaction analysis. The philicities of the HaB partners were further verified by the analysis of electron localization function projections, electron density/electrostatic potential profiles along the I···N bond paths, natural bond orbital analysis, and the natural population analysis or atoms-in-molecules charge sums in model systems.
AB - Two diphenyliodonium tetracyanidometallates, [Ph2I]2[M(CN)4] (M = Ni and Pd), were prepared through anion metathesis. Their X-ray structural analyses show that the structure-defining contact for both crystals is the charge-assisted I···N halogen bond (HaB) formed between the I atom of the iodonium cations and the N atoms of the CN-ligands. These HaBs assemble the bidentate and 90°-orienting HaB donor Ph2I+and the tetradentate, square planar, and 90/180°-orienting HaB acceptors [M(CN)4]2-into supramolecular rectangles, which further assemble into infinite chains by sharing the vertexes occupied by the [M(CN)4]2-anions. The noncovalent nature of these contacts was confirmed by density functional theory calculations (M06/def2-TZVP) followed by combined topological analysis of the electron density distribution in the quantum theory of the atoms-in-molecules approach and noncovalent interaction analysis. The philicities of the HaB partners were further verified by the analysis of electron localization function projections, electron density/electrostatic potential profiles along the I···N bond paths, natural bond orbital analysis, and the natural population analysis or atoms-in-molecules charge sums in model systems.
UR - http://www.scopus.com/inward/record.url?scp=85127623336&partnerID=8YFLogxK
UR - https://www.mendeley.com/catalogue/9c053c4e-524a-3137-9f97-69670b81e93a/
U2 - 10.1021/acs.cgd.2c00175
DO - 10.1021/acs.cgd.2c00175
M3 - Article
AN - SCOPUS:85127623336
VL - 22
SP - 2749
EP - 2758
JO - Crystal Growth and Design
JF - Crystal Growth and Design
SN - 1528-7483
IS - 4
ER -
ID: 100021360