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Noncovalent spodium bonding boosts the phosphorescence of platinum emitters.

Chalcogen bonding which does not include σ-hole interaction.

A single-crystal X-ray diffraction (XRD) study of diaryliodonium tetrachloroaurates (or, in the recent terminology, tetrachloridoaurates), [(

Cyclometalated platinum(II) complexes [Pt(ppy)Cl(CNAr)] (ppy = 2-phenylpyridinato-C

Imidoylamidinate-based heteroleptic bis(2-phenylbenzothiazole)iridium(III) and -rhodium(III) complexes [(

Three isomorphic cocrystals were obtained via the crystallization of [PPN][AuCl

The {dz2-MIIS4} (M = Ni, Pd, Pt) moieties function as integrated five-center acceptors toward a π-hole of an electron-deficient arene furnishing the reverse sandwich structures.

An efficient synthetic strategy that includes protection–modification–deprotection consequence was successfully developed to obtain novel water-soluble, amphiphilic, surface-active maltodextrin-based glycosilicones.

Porous architectures characterized by parallel channels arranged in honeycomb or rectangular patterns are identified in two polymorphic crystals of a zwitterionic 4-(aryliodonio)-benzenesulfonate. The channels are filled with disordered water molecules which can be reversibly removed on heating. Consistent with the remarkable strength and directionality of the halogen bonds (XBs) driving the crystal packing formation, the porous structure is stable and fully preserved on almost quantitative removal and readsorption of water. The porous systems described here are the first reported cases of one-component 3D organic frameworks whose assembly is driven by XB only (XOFs). These systems are a proof of concept for the ability of zwitterionic aryliodonium tectons in affording robust one-component 3D XOFs. The high directionality and strength of the XBs formed by these zwitterions and the geometrical constraints resulting from the tendency of their hypervalent iodine atoms to act as bidentate XB donors might be key factors in determining this ability.

Gold(i)-catalyzed highly regioselective hydration of alkynylsulfones comprises an efficient 100% atom-economic route to β-ketosulfones.

Two adjacent CuI-bound isocyanide groups exhibit nucleophilic properties induced by a π-donating d10[CuI] center and function as an integrated two-center halogen bond acceptor forming bifurcated μ2-X⋯(C,C) halogen bonds.

The half-lantern PtII2 complexes [Pt(CN)(μ-SN)]2 (HCN = 2-phenylbenzothiazolate 1; 2-naphtylbenzothiazolate 2; HSN = 2-thiopyridine) were crystallized with such electron-deficient arenes as hexafluorobenzene (C6F6) and octafluoroanthraquinone (OFA) to give cocrystals 1·C6F6,...

Gold(I)-catalyzed [4 + 2] cycloaddition of indolylynamides and cyanamides (aminonitriles) is an efficient redox-neutral and atom-economic route to diversely substituted 1,3-diamino-β-carbolines. The protocol operates under mild conditions (Ph3PAuNTf2 5 mol %, DCE, 60 °C) with a good tolerance to functional groups (23 examples and yields up to 98%). The obtained β-carboline systems represent a versatile synthetic platform with modifiable substituents for successive functionalizations. Control experiments indicate the crucial role of both the nature of reactants and the identity of employed catalysts in the developed cycloaddition.

The co-crystallization of the lead(II) complex [Pb(S2CNEt2)2] with tetraiodoethylene (C2I4) gave the co-crystal, [Pb(S2CNEt2)2]∙½C2I4, whose X-ray structure exhibits only a small change of the crystal parameters than those in the parent [Pb(S2CNEt2)2]. The supramolecular organization of the co-crystal is largely determined by an interplay between Pb⋯S tetrel bonding (TeB) and I⋯S halogen bonding (HaB) with comparable contributions from these non-covalent contacts; the TeBs observed in the parent complex, [Pb(S2CNEt2)2], remain unchanged in the co-crystal. An analysis of the theoretical calculation data, performed for the crystal and cluster models of [Pb(S2CNEt2)2]∙½C2I4, revealed the non-covalent nature of the Pb⋯S TeB (−5.41 and −7.78 kcal/mol) and I⋯S HaB (−7.26 and −11.37 kcal/mol) interactions and indicate that in the co-crystal these non-covalent forces are similar in energy.

The architecture of transparent contacts is of utmost importance for creation of efficient flexible light-emitting devices (LEDs) and other deformable electronic devices. We successfully combined the newly synthesized transparent and durable silicone rubbers and the semiconductor materials with original fabrication methods to design LEDs and demonstrate their significant flexibility. We developed electrodes based on a composite GaP nanowire-phenylethyl-functionalized silicone rubber membrane, improved with single-walled carbon nanotube films for a hybrid poly(ethylene oxide)-metal-halide perovskite (CsPbBr3) flexible green LED. The proposed approach provides a novel platform for fabrication of flexible hybrid optoelectronic devices.

The gold-catalyzed reaction between benzofuroxans, functioning as nitrene transfer reagents, and N-allylynamides leads to 3-azabicyclo[3.1.0]hexan-2-imines. This highly selective annulation proceeds smoothly under mild conditions (5 mol % Ph3PAuNTf2, PhCl, 60 °C) and exhibits high functional group tolerance (21 examples, ≤96% yields). The obtained cyclopropanated products represent a useful synthetic platform with an easily modulated substitution pattern as illustrated by their postmodifications. Intramolecular cyclopropanation of gold α-imino carbene intermediates is suggested as a key step of the catalytic cycle.

A series of 2,5-dibromo-3-R-thiophenes (R = COONa 1, CN 2, CONH2 3, CON(H)Me 4, CON(H)Bn 5, CON(CH2CH2)2O 6, CON(H)NH2 7, CON(H)OH 8) were prepared and studied via high-resolution ESI-MS, 1H and 13...

A family of the C,N-cyclometalated species [Pt(ppy)Cl(PPh3)], [Pt(ppy)Cl(CNCy)], [Pt(ppy)(CNCy)(PPh3)](OTf), and [Pt(ppy)(CNCy)2](BF4) (ppy = 2-phenylpyridinato-C2,N; Cy = cyclohexyl) was generated...

Three diaryliodonium tetrachloroaurates(III), [Ar1IAr2][AuCl4] (Ar1/Ar2 = Ph/Ph (1), Ph/Mes (2), o-(C6H4)2 (3)), were obtained as solids (62–80%) by the metathetical reaction of [Ar1IAr2](CF3CO2) a...

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.

Co-crystallization of dithiocarbamate complexes [MII(S2CNEt2)2] (M = Cu 1, Ni 2, Pd 3, Pt 4) and 1,3,5-triiodotrifluorobenzene (FIB) gives an isomorphic series of (1–4)·2FIB co-crystals exhibiting quadruple Cu/Ni/Pd/Pt isostructural exchange. In the structures of (1–4)·2FIB, the halogen-bonded C–I⋯M (Ni, Pd, Pt) and semicoordination M⋯I–C (Cu) metal-involving contacts were identified by X-ray diffractometry and their nature was verified theoretically. The directionality of the Iσ-hole⋯d2zMII and MII⋯Ielectron belt interactions depends on the identity of a metal center: on going from a rather electrophilic CuII to substantially more nucleophilic NiII, PdII, and PtII centers, we observed the electron belt-to-σ-hole switch of a noncovalently bound iodine(I) of FIB and, correspondingly, its shift from semicoordination to halogen bonding. The negative values of the electrostatic potentials (given in parentheses) were estimated for all metal centers and they decrease in the order CuII (−8.8) > NiII (−24.5) > PdII (−28.6) > PtII (−33.3 kcal mol−1). Despite the negative potentials at all MIIs, the semicoordinative contact Cu⋯I was established by the recognition of the LP(I) → LP*(Cu) charge transfer using natural bond orbital (NBO) analysis and the comparison of electron density (ED) and electrostatic potential (ESP) minima positions along the I⋯Cu bond paths. In the case of the rather nucleophilic (although positively charged) PdII and PtII centers, the contacts C–I⋯d2z[Pd] and C–I⋯d2z[Pt] can be attributed to the unconventional metal-involving halogen bonding; these contacts are among the strongest (4.30 and 5.42 kcal mol−1, correspondingly) between any metal center and iodine(I)-based σ-hole donors.

Cocrystallization of the nitrosoguanidinate complexes [Ni{NH═C(NR2)NN(O)}2] (R2 = Me2 (1), Me/Ph (2), C5H10 (3)) with 1,2-diiodotetrafluorobenzene (1,2-FIB), 1,4-diiodotetrafluorobenzene (1,4-FIB),...

The complex [Ni(S2COEt)2] (1) and 1,4-diiodotertafluorobenzene (1,4-FIB) or 1,3,5-triiodotrifluorobenzene (1,3,5-FIB) were cocrystallized to form solid adducts 1·2(1,4-FIB) and 1·2(1,3,5-FIB), resp...

Crystallization of newly prepared copper(II) clusters [Cu4X6O(NCNMe2)4] (X = Cl 1 or Br 2) from toluene and styrene solutions afforded crystalline adducts 1·4PhMe, 1·4PhCH═CH2, 2·4PhMe, and 2·4PhCH═CH2, which were characterized by physicochemical methods including single-crystal X-ray diffraction. Inspection of the X-ray structures of (1–2)·4(arene) and the appropriate Hirshfeld molecular surface analysis allowed the recognition of the previously unreported π-hole···arene interactions involving the cyanamide ligands. The presence of these interactions and their structure-directing character was confirmed theoretically by density functional theory calculations including molecular electrostatic potential, energy decomposition, and atoms-in-molecules analyses. The observed π-hole···π interaction between coordinated cyanamide and arene moieties in the adducts exhibits a contribution of π-hole···σ(C–Haryl) interaction. Analysis of the Cambridge Structure Database revealed that the cyanamide···arene separations in the [Cu4X6O(NCNMe2)4]·4(arene) systems are among the shortest found for all reported cyanamide structures.

Perfluorinated arenes (benzeneF derivatives, diphenylF, naphtaleneF) were converted into X-perfluoroarenes (X = Br, I) via the developed one-pot protocol based on [Fe(acetylacetonate)3]-assisted C–...

Two phosphorescent PtII-based cyclometalated complexes were co-crystallized with perfluorinated arenes to give 1:1 co-crystals. The X-ray study revealed that each of the complexes is embraced by ar...