Photoredox-catalyzed arylation of isonitriles by diaryliodonium salts towards benzamides.

The arylation of isonitriles by diaryliodonium salts under photoredox conditions has been proposed for the first time. The suggested procedure allows preparing a broad range of benzamides using both symmetric and unsymmetric diaryliodonium salts under mild conditions. A plausible mechanism for the reaction and the selectivity of aryl transfer (in case of unsymmetrical iodonium salts) were studied.

Hyperuniform Mesoporous Gold Films Coated with Halogen-Bonding Metal-Organic Frameworks for Selective Raman Sensing of Chlorinated Hydrocarbons.

The selective detection of chlorinated aromatic hydrocarbons (CAHs) in environmental samples is challenging due to matrix interference effects. We report a surface-enhanced Raman spectroscopy (SERS) sensor that combines mesoporous Au films with UiO-66-I metal-organic framework (MOF) coatings to achieve the selective detection of CAHs. We show that mesoporous Au films can be considered hyperuniform two-dimensional (2D) materials where long-range correlations and local disorder assist in electromagnetic hotspot formation for SERS.

Photolysis of labile bonds towards radical generation: case study of alkyl verdazyls.

Two series of stable verdazyl radical derivatives, specifically 1,2,4,6-substituted-1,4-dihydro-1,2,4,5-tetrazin-3(2)-ones (also called "alkylverdazyls" or "AlkVZs"), were systematically investigated in photoactivated C-N bond homolysis. In-depth evaluation of their mechanisms indicated that several factors played a pivotal role in the generation of radicals during photon absorbance. From quantum chemical calculations, it was found that the most influential factor is the generation of charge-separated excited states, where one electron is located at the verdazyl moiety and the second one is distributed at the alkyl part.

Revising Model Reactions in Plasmonic Chemistry: From Nitrothiophenol Coupling to Alkoxyamine Homolysis.

The progress in plasmonic chemistry requires research on energy transfer, mechanisms, and materials discovery. In this pursuit, there are >3000 papers applying the azo coupling of 4-nitrothiophenol (PNTP) as a model reaction. Here, we challenge the status of this reaction as a model due to experimental evidence of thiol desorption during plasmon excitation using laser irradiation monitored by X-ray photoelectron spectroscopy (XPS) as an analytic technique.

Controlled Mono- and Double-Insertion of Sulfonamide Fragments into Ni-S Bonds of Nickel(II) Dithiocarbamate Complexes via Sulfonyl Azide Reactivity.

A novel approach for controlled mono- and double-insertion of sulfonamide fragments into Ni-S bonds of [Ni(SCNR)] complexes has been developed using aryl and alkyl sulfonyl azides as sulfonamide sources. The reaction selectivity is governed by the choice of solvent (hexafluoro-2-propanol for the monoinsertion versus isopropanol for the double-insertion) and temperature (50 and 80 °C, respectively). This method provides convenient access to previously unreported monoinsertion products [NiL(SCNR)] along with the double-insertion complexes [NiL] (L = NSO(R')SNR) under mild conditions.

Copper-catalyzed -arylation of 1,2,4-oxadiazin-5(6)-ones by diaryliodonium salts.

Herein, we developed a new synthetic approach for the preparation of -arylated 1,2,4-oxadiazin-5(6)-ones by direct arylation with diaryliodonium salts. The reaction with symmetrical diaryliodonium salts using CuI as a catalyst proceeded in toluene in the presence of DIPEA at 60 °C with the formation of the desired products in isolated yields of 46 to 97% (20 examples). The use of more readily available unsymmetrical diaryliodonium salts required higher reaction temperatures (up to 100 °C) to achieve similar yields.

Electrochemical Switching of Laser-Induced Graphene/Polymer Composites for Tunable Electronics.

Laser reduction of graphene oxide (GO) is a promising approach for achieving flexible, robust, and electrically conductive graphene/polymer composites. Resulting composite materials show significant technological potential for energy storage, sensing, and bioelectronics. However, in the case of insulating polymers, the properties of electrodes show severely limited performance.

The Ground State of Multispin Systems Based on Verdazyl and Nitrene Radicals: An EPR and Quantum-Chemical Study.

In this study, low-temperature EPR spectroscopy and quantum-chemical techniques were employed to investigate multispin systems─1,5-diphenyl-3-(3-nitrenophenyl)-6-oxoverdazyl and 1,5-diphenyl-3-(4-nitrenophenyl)-6-oxoverdazyl─that contain a nitrene center at either a - or -position, respectively. Ground states and magnetic zero-field splitting (ZFS) parameters of these multispin systems were determined by experimental and computational methods. The results indicated that the high-spin quartet state is a ground state, and the quartet-doublet energy gap is close to 10 kcal/mol for the -position of the nitrene group, with ZFS parameters = 0.

N-Heterocycle-coordinated -iodanes as IBX alternatives for alcohol oxidations.

We report the synthesis of novel N-coordinated -iodanes as a unique class of hypervalent iodine compounds. X-ray diffraction analysis revealed their intriguing (pseudo)cyclic structure, showcasing distinctive N⋯I-secondary bonding interactions. We demonstrate the generation of reactive diacetoxy derivatives, which exhibits remarkable efficacy in alcohol oxidation reactions.

Photochemistry dominates over photothermal effects in the laser-induced reduction of graphene oxide by visible light.

Graphene oxide (GO) possesses specific properties that are revolutionizing materials science, with applications extending from flexible electronics to advanced nanotechnology. A key method for harnessing GO's potential is its laser-induced reduction, yet the exact mechanisms - photothermal versus photochemical effects - remain unclear. Herein, we discover the dominant role of photochemical reactions in the laser reduction of GO under visible light, challenging the prevailing assumption that photothermal effects are dominant.

Key-to-lock halogen bond-based tetragonal pyramidal association of iodonium cations with the lacune rims of beta-octamolybdate.

The structure-directing "key-to-lock" interaction of double σ-(I)-hole donating iodonium cations with the O-flanked pseudo-lacune rims of [β-MoO] gives halogen-bonded iodonium-beta-octamolybate supramolecular associates. In the occurrence of their tetragonal pyramidal motifs, deep and broad σ-(I)-holes of a cation recognize the molybdate backbone, which provides an electronic pool localized around the two lacunae. The halogen-bonded I⋯O linkages in the structures were thoroughly studied computationally and classified as two-center, three-center bifurcated, and unconventional "orthogonal" I⋯O halogen bonds.

Oxidation Performance of Nano-Layered (AlTiZrHfTa)N/SiN Coatings Deposited by Reactive Magnetron Sputtering.

This work uses the direct current magnetron sputtering (DCMS) of equi-atomic (AlTiZrHfTa) and Si targets in dynamic sweep mode to deposit nano-layered (AlTiZrHfTa)N/SiN refractory high-entropy coatings (RHECs). Transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) are used to investigate the effect of Si addition on the oxidation behavior of the nano-layered coatings. The Si-free nitride coating exhibits FCC structure and columnar morphology, while the Si-doped nitride coatings present a FCC (AlTiZrHfTa)N/amorphous-SiN nano-layered architecture.

Toward New Horizons in Verdazyl-Nitroxide High-Spin Systems: Thermally Robust Tetraradical with Quintet Ground State.

High-spin organic tetraradicals with significant intramolecular exchange interactions have high potential for advanced technological applications and fundamental research, but examples reported to date exhibit limited stability and processability. In this work, we designed the first tetraradical based on an oxoverdazyl core and nitronyl nitroxide radicals and successfully synthesized it using a palladium-catalyzed cross-coupling reaction of an oxoverdazyl radical bearing three iodo-phenylene moieties with a gold(I) nitronyl nitroxide-2-ide complex in the presence of a recently developed efficient catalytic system. The molecular and crystal structures of the tetraradical were confirmed by single crystal X-ray diffraction analysis.

Preparation and X-ray Structural Study of Dibenzobromolium and Dibenzochlorolium Derivatives.

Various five-membered cyclic dibenzobromolium salts (dibenzo[,]bromol-5-ium chloride, nitrate, hydrogen sulfate, dihydrogen phosphate, trifluoroacetate, and tetrafluoroborate) were prepared by diazotization-cyclization of 2'-bromo-[1,1'-biphenyl]-2-amine in solution of appropriate acids. The chlorolium analogues (iodide, trifluoroacetate, and tetrafluoroborate) were obtained by a similar procedure. Additional dibenzohalolium derivatives (dibenzo[,]bromol-5-ium and dibenzo[,]chlorol-5-ium azides, bis(trifluoromethanesulfonyl)imidates, thiocyanates, and trifluoromethanesulfonates) were prepared by anion exchange.

Halogen Bond-Involving Self-Assembly of Iodonium Carboxylates: Adding a Dimension to Supramolecular Architecture.

We designed 0D, 1D, and 2D supramolecular assemblies made of diaryliodonium salts (functioning as double σ-hole donors) and carboxylates (as σ-hole acceptors). The association was based on two charge-supported halogen bonds (XB), which occurred between I sites of the iodonium cations and the carboxylate anions. The sequential introduction of the carboxylic groups in the aryl ring of the benzoic acid added a dimension to the 0D supramolecular organization of the benzoate, which furnished 1D-chained and 2D-layered structures when terephthalate and trimesate anions, correspondingly, were applied as XB acceptors.

Metal-free and atom-efficient protocol for diarylation of selenocyanate by diaryliodonium salts.

We developed an atom- and reaction mass efficient strategy for the preparation of diarylselenides using iodonium salts as reactants. The developed approach allows the obtaining of diarylselenides from the corresponding trimethoxyphenyl-substituted iodonium salts a two-step one-pot reaction sequence. The proposed metal-free methodology is based on the involvement of both iodonium aryl groups for diarylation.

"Functional upcycling" of polymer waste towards the design of new materials.

Diversification of polymer waste recycling is one of the solutions to improve the current environmental scenario. Upcycling is a promising strategy for converting polymer waste into molecular intermediates and high-value products. Although the catalytic transformations into small molecules have been actively discussed, the methods and characteristics of upcycling into new materials have not yet been addressed.

Noncovalent Chelation by Halogen Bonding in the Design of Metal-Containing Arrays: Assembly of Double σ-Hole Donating Halolium with Cu-Containing O,O-Donors.

Five new copper(I) complexes─composed of the paired dibenzohalolium and [CuL] (L = 1,2,4-oxadiazolate) counterions in which O,O-atoms of the anion are simultaneously linked to the halogen atom─were generated and isolated as the solid via the three-component reaction between [Cu(MeCN)](BF), sodium 1,2,4-oxadiazolates, and dibenzohalolium triflates (or trifluoroacetates). This reaction is different from the previously reported Cu-catalyzed arylation of 1,2,4-oxadiazolones by diaryliodonium salts. Inspection of the solid-state X-ray structures of the complexes revealed the strong three-center X···O,O (X = Br, I) halogen bonding occurred between the oxadiazolate moieties and dibenzohalolium cation.

Sweetened Alkylated Verdazyls Effectively Kill Cancer Cells under Light Irradiation.

The development of novel photo-dynamic therapy (PDT) agents enabling to treat the oxygen-deficient tumors is the emerging tasks for the modern medicinal chemistry. Herein, we describe the design and preparation of water-soluble agents for PDT which generate active radical species upon light irradiation. Two conjugates of carbohydrates with 1,2,4,6-substituted-1,4-dihydro-1,2,4,5-tetrazin-3(2H)-ones (AlkVZs) demonstrated high oxygen-independent cytotoxicity on PC-3 and Jurkat cancer cells under light irradiation combining with low toxicity in the dark.

Ligand-free Ullmann-type arylation of oxazolidinones by diaryliodonium salts.

The arylation of azaheterocycles can be considered as one of the most important processes for the preparation of various biologically active compounds. In the present work, we describe a method for the copper-catalyzed -arylation of hindered oxazolidinones using diaryliodonium salts. The method succeeds in good to excellent yields for the arylation of 4-alkyloxazolidinones, including sterically hindered isopropyl- and -butyl-substituted.

Halogen Bonding Involving Gold Nucleophiles in Different Oxidation States.

A single-crystal X-ray diffraction (XRD) study of diaryliodonium tetrachloroaurates (or, in the recent terminology, tetrachloridoaurates), [(-XCH)I][AuCl] (X = Cl, ; Br, ), was performed for (the structure is denoted as to show similarity with the isomorphic structure ) and two polymorphs─ (obtained from MeOH) and (from 1,2-CHCl). Examination of the XRD data for these three structures revealed 2-center C-X···Au (X = Cl and Br) and 3-center bifurcated C-Br···(-) halogen bonding (abbreviated as XB) between the -Cl or -Br atoms of the diaryliodonium cations and the gold(III) atom of [AuCl]. The noncovalent nature of Au-involving interactions, the nucleophilicity of the gold(III) atoms, and the electrophilic role of -X atoms of the diaryliodonium cations in the XBs were studied by a set of complementary computational methods.

Surface Filtration in Mesoporous Au Films Decorated by Ag Nanoparticles for Solving SERS Sensing Small Molecules in Living Cells.

For surface-enhanced Raman spectroscopy (SERS) sensing of small molecules in the presence of living cells, biofouling and blocking of plasmonic centers are key challenges. Here, we have developed a mesoporous Au (AuM) film coated with a Ag nanoparticles (NPs) as a plasmonic sensor (AuM@Ag) to analyze aromatic thiols, which is an example of a small molecule, in the presence of a living cell strain (e.g.

The Effect of Sibunit Carbon Surface Modification with Diazonium Tosylate Salts of Pd and Pd-Au Catalysts on Furfural Hydrogenation.

Herein, we investigated the effect of the support modification (Sibunit carbon) with diazonium salts of Pd and Pd-Au catalysts on furfural hydrogenation under 5 bars of H and 50 °C. To this end, the surface of Sibunit (Cp) was modified with butyl (Cp-Butyl), carboxyl (Cp-COOH) and amino groups (Cp-NH) using corresponding diazonium salts. The catalysts were synthesized by the sol immobilization method.