TY - JOUR
T1 - Highly polar stacking interactions wrap inorganics in organics
T2 - Lone-pair-π-hole interactions between the PdO4core and electron-deficient arenes
AU - Torubaev, Yury V.
AU - Skabitsky, Ivan V.
AU - Rozhkov, Anton V.
AU - Galmés, Bartomeu
AU - Frontera, Antonio
AU - Kukushkin, Vadim Yu
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. 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.
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. 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.
UR - http://www.scopus.com/inward/record.url?scp=85119931117&partnerID=8YFLogxK
U2 - 10.1039/d1qi01067k
DO - 10.1039/d1qi01067k
M3 - Article
AN - SCOPUS:85119931117
SN - 2052-1545
VL - 8
SP - 4965
EP - 4975
JO - Inorganic Chemistry Frontiers
JF - Inorganic Chemistry Frontiers
IS - 23
ER -