Issue 23, 2021

Highly polar stacking interactions wrap inorganics in organics: lone-pair–π-hole interactions between the PdO4 core and electron-deficient arenes

Abstract

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. Significant intermolecular noncovalent interactions were verified by a density functional theory study, molecular electrostatic potential and Hirshfeld surface analyses, a combined QTAIM/NCPlot approach, and NBO and energy framework calculations. In five out of six structures, the aromatic rings coupled with cluster [Pd3] via lone pair–π-(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.

Graphical abstract: Highly polar stacking interactions wrap inorganics in organics: lone-pair–π-hole interactions between the PdO4 core and electron-deficient arenes

Supplementary files

Article information

Article type
Research Article
Submitted
21 avq 2021
Accepted
06 okt 2021
First published
06 okt 2021

Inorg. Chem. Front., 2021,8, 4965-4975

Highly polar stacking interactions wrap inorganics in organics: lone-pair–π-hole interactions between the PdO4 core and electron-deficient arenes

Y. V. Torubaev, I. V. Skabitsky, A. V. Rozhkov, B. Galmés, A. Frontera and V. Yu. Kukushkin, Inorg. Chem. Front., 2021, 8, 4965 DOI: 10.1039/D1QI01067K

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