Highly polar stacking interactions wrap inorganics in organics: Lone-pair-π-hole interactions between the PdO 4core and electron-deficient arenes

Ю.Н. Торубаев, И.В. Скабитский, Антон Викторович Рожков, B. Galmes, Antonio Frontera, Вадим Юрьевич Кукушкин

Результат исследований: Научные публикации в периодических изданияхстатьярецензирование

5 Цитирования (Scopus)


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.
Язык оригиналаанглийский
Страницы (с-по)4965-4975
Число страниц11
ЖурналInorganic Chemistry Frontiers
Номер выпуска23
Ранняя дата в режиме онлайн6 окт 2021
СостояниеОпубликовано - 7 дек 2021

Предметные области Scopus

  • Неорганическая химия