Research output: Contribution to journal › Article › peer-review
Highly polar stacking interactions wrap inorganics in organics : Lone-pair-π-hole interactions between the PdO 4core and electron-deficient arenes. / Торубаев, Ю.Н.; Скабитский, И.В.; Рожков, Антон Викторович; Galmes, B.; Frontera, Antonio; Кукушкин, Вадим Юрьевич.
In: Inorganic Chemistry Frontiers, Vol. 8, No. 23, 07.12.2021, p. 4965-4975.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Highly polar stacking interactions wrap inorganics in organics
T2 - Lone-pair-π-hole interactions between the PdO 4core and electron-deficient arenes
AU - Торубаев, Ю.Н.
AU - Скабитский, И.В.
AU - Рожков, Антон Викторович
AU - Galmes, B.
AU - Frontera, Antonio
AU - Кукушкин, Вадим Юрьевич
N1 - Publisher Copyright: © the Partner Organisations.
PY - 2021/12/7
Y1 - 2021/12/7
N2 - Cocrystallization of the palladium acetate cluster Pd3(OAc)6 (abbreviated as [Pd3]) with electron-deficient iodine(I)-based perfluoroarenes (ArFI: iodopentafluorobenzene, 4-iodoheptafluorotoluene, 1,4-diiodotetrafluorobenzene, 1,2-diiodotetrafluorobenzene, and octafluoro-4,4’-diiodo-1,1-biphenyl) and iodine-free octafluoronaphthalene gave a series of six cocrystals [Pd3]·(arene) studied by single-crystal X-ray diffractometry. The significant intermolecular noncovalent interactions were verified by a density functional theory study, molecular electrostatic potential and Hirshfeld surface analyses, combined QTAIM/NCPlot approach, and energy framework calculations. In five out of six structures, the aromatic rings coupled with cluster [Pd3] via lone pair–-(ArF)-hole interactions. The iodine-containing arenes, ArFI, were additionally involved in halogen bonding with carboxylate O centers, but inorganic-organic stacking still remained the structure-determining interaction. In the stacking, the electron-rich PdO4 plane behaved as a five-center nucleophile providing oxygen lone pairs in addition to the dz2-PdII orbital; this plane complemented the π-acidic surface of the arenes, affording highly polar circular stacking, where organics wrapped inorganics.
AB - Cocrystallization of the palladium acetate cluster Pd3(OAc)6 (abbreviated as [Pd3]) with electron-deficient iodine(I)-based perfluoroarenes (ArFI: iodopentafluorobenzene, 4-iodoheptafluorotoluene, 1,4-diiodotetrafluorobenzene, 1,2-diiodotetrafluorobenzene, and octafluoro-4,4’-diiodo-1,1-biphenyl) and iodine-free octafluoronaphthalene gave a series of six cocrystals [Pd3]·(arene) studied by single-crystal X-ray diffractometry. The significant intermolecular noncovalent interactions were verified by a density functional theory study, molecular electrostatic potential and Hirshfeld surface analyses, combined QTAIM/NCPlot approach, and energy framework calculations. In five out of six structures, the aromatic rings coupled with cluster [Pd3] via lone pair–-(ArF)-hole interactions. The iodine-containing arenes, ArFI, were additionally involved in halogen bonding with carboxylate O centers, but inorganic-organic stacking still remained the structure-determining interaction. In the stacking, the electron-rich PdO4 plane behaved as a five-center nucleophile providing oxygen lone pairs in addition to the dz2-PdII orbital; this plane complemented the π-acidic surface of the arenes, affording highly polar circular stacking, where organics wrapped inorganics.
KW - ADDUCT
KW - CATALYSIS
KW - CHEMISTRY
KW - COMPLEX
KW - CUBIC CLUSTER PD6CL12
KW - ENERGY FRAMEWORKS
KW - HALOGEN
KW - NONCOVALENT INTERACTIONS
KW - SUPRAMOLECULAR AGGREGATION
KW - WEAK-INTERACTIONS
UR - http://www.scopus.com/inward/record.url?scp=85119931117&partnerID=8YFLogxK
UR - https://www.mendeley.com/catalogue/82662e4a-aa5e-3bac-a9e3-8a9db7decdf4/
U2 - 10.1039/d1qi01067k
DO - 10.1039/d1qi01067k
M3 - Article
VL - 8
SP - 4965
EP - 4975
JO - Inorganic Chemistry Frontiers
JF - Inorganic Chemistry Frontiers
SN - 2052-1545
IS - 23
ER -
ID: 87338061