Multifunctional Dy Complexes with Triphenylmethanolates: Structural Diversity, Luminescence, and Magnetic Relaxation.

The coordination environment of magneto-luminescent Dy-based Single-Molecule Magnets (SMM) is a crucial factor influencing both magnetic and luminescent properties. In this work, we explore how triphenylmethanolate (PhCO), in combination with other ligands, can modulate the structure and, therefore, the magnetic properties of Dy-based SMM. Using triphenylmethanolate in combination with THF and pyridine (Py) as co-ligands, we synthesized a series of mononuclear -[Dy(OCPh)(THF)][BPh]·(2,6-MeCHN) (), -Dy(OCPh)(THF) (), -Dy(OCPh)(py) () and dinuclear [(PhCO)Dy(THF){(μ-Cl)Li(THF)}μ-Cl] () complexes where the Dy ion presents five- or six-coordinate geometries.

Activation of CO, CS, and COS by α-Diimine-Stabilized Gallylenes.

Several gallylenes [LGaM(THF)] stabilized by an α-diimine ligand (L=[(2,6-iPrCH)NC(Ph)] ; M=Li, n=3, 3-Li; M=Na, n=4, 3-Na; M=K, n=1, 3-K) were prepared, which display diverse reactivities toward carbon dioxide and its sulfurized analogues. The reaction of 3 with CO yielded a trimeric carbonate complex [{LGa(CO)}{μ-K(THF)}] (4) and a dinuclear oxo-carbonate complex [K(THF)][LGa(μ-CO)(μ-O)GaL] (5) in one pot through reductive disproportionation of CO. For CS, two ethenetetrathiolate gallium complexes, [M(Solv)][LGa(μ-CS)GaL] (M=Na, Solv=THF, 6; M=K, Solv=DME, 7), were obtained via reductive coupling of CS.

Expression of concern: Valence tautomeric interconversion of bis-dioxolene cobalt complex with imino-pyridine functionalized by TEMPO moiety in solid solutions with isostructural nickel analogue: phase transitions and monocrystal destruction.

Expression of concern for 'Valence tautomeric interconversion of bis-dioxolene cobalt complex with imino-pyridine functionalized by TEMPO moiety in solid solutions with isostructural nickel analogue: phase transitions and monocrystal destruction' by Michael P. Bubnov , , 2024, , 9151-9160, https://doi.org/10.

Reactions of an Anionic Gallylene with Azobenzene or Azide Compounds Through C(sp)-H and C(sp)-H Activation.

The activation of inert C-H bonds remains a challenge in current chemistry. Here, we report the excellent reactivity of the anionic gallylene species [LGa:][Na(THF)] (L = [(2,6-PrCH)NC(CH)], ) that allows the selective activation one sp C-H bond of several azobenzene and azide derivatives at ambient temperature, with the transfer of the hydrogen atom to one of the nitrogen atoms. The process leads to the formation of the aryl amido products [LGa-κN,C-PhNN(H)(-R-CH)][Na(solvent)] (, R = H solvent = DME (1,2-Dimethoxyethane); , R = -OMe, solvent = DME; , R = -NMe solvent = THF), [LGa-κN,C-(-CH-CH)NN(H)(-CH-CH)][Na(15-C-5)] () with new Ga-C and Ga-N bonds.

Hydro-coupling of isocyanates promoted by 1,2-bis(arylimino)acenaphthene aluminum hydrides.

The interaction of aluminum hydrides [(dpp-bian)AlH] (1) and [(Ar-bian)AlH(THF)] (2) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene; Ar-bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene) with isocyanates RNCO (R = Ph, Cy, 3,5-ClPh) proceeds insertion of two molecules of isocyanates into each Al-H bond with the formation of unique Al carboxamides [(Ar-bian)Al{OC(H)N(R)C(NR)O}] (Ar = dpp, R = Ph, 3; Ar = Ar, R = Ph, 4; Ar = Ar, R = Cy, 5; Ar = Ar, R = 3,5-ClCH, 6). In contrast, the reactions of 1 and 2 with an excess of -butylisocyanate afford formimidate derivatives [(Ar-bian)Al{OC(H)N(Bu)}] (Ar = dpp, 7; Ar = Ar, 8). The reactions of ,'-dicyclohexylcarbodiimide with 1 and 2 give [(dpp-bian)Al{(NCy)CH}] (9) and [(Ar-bian)Al(H){(NCy)CH}] (10), correspondingly.

Synthesis, electrochemical properties, and antioxidant activity of sterically hindered catechols with 1,3,4-oxadiazole, 1,2,4-triazole, thiazole or pyridine fragments.

A series of new RS-, RS-CH- and RN-CH-functionalized сatechols with heterocyclic fragments such as 1,3,4-oxadiazole, 1,2,4-triazole, thiazole, or pyridine were synthesized by the reaction of 3,5-di--butyl--benzoquinone or 3,5-di--butyl-6-methoxymethylcatechol with different heterocyclic thiols. The S-functionalized catechols were prepared by the Michael reaction from 3,5-di--butyl--benzoquinone and the corresponding thiols. The starting reagents such as substituted 1,3,4-oxadiazole-2-thiols and 4-triazole-3-thiols are characterized by thiol-thione tautomerism, therefore their reactions with 3,5-di--butyl-6-methoxymethylcatechol can proceed at the sulfur or nitrogen atom.

Reduction of Ketones and Coupling of Ketyls by a Zn-Zn-Bonded Compound.

The α-diimine-ligated Zn-Zn-bonded compound [K(THF)][LZn-ZnL] (, L = [(2,6-PrCH)NC(Me)]) displays diverse reactivities toward a variety of ketones. In the reaction of with benzophenone or 4,4'-di--butylbenzophenone, a multielectron transfer process was observed to give bimetallic (Zn/K) complexes with both ketyl radical fragments and C-C coupled pinacolate moieties (products and ). In contrast, treating with 9-fluorenone only afforded pinacolate complex .

Soluble Fluorinated Cardo Copolyimide as an Effective Additive to Photopolymerizable Compositions Based on Di(meth)acrylates: Application for Highly Thermostable Primary Protective Coating of Silica Optical Fiber.

The development of photocurable compositions is in high demand for the manufacture of functional materials for electronics, optics, medicine, energy, etc. The properties of the final photo-cured material are primarily determined by the initial mixture, which needs to be tuned for each application. In this study we propose to use simple systems based on di(meth)acrylate, polyimide and photoinitiator for the preparation of new photo-curable compositions.

Valence tautomeric interconversion of bis-dioxolene cobalt complex with imino-pyridine functionalized by TEMPO moiety in solid solutions with isostructural nickel analogue: phase transitions and monocrystal destruction.

Valence tautomeric complexes (VT) are promising systems for creating molecular devices. From this viewpoint, valence tautomeric complexes with a hysteresis loop on the magnetic curve are of special interest as potential memory elements. The hysteresis loop is a consequence of retarded structural rearrangements which investigation is an actual problem.

Gradual solid-state redox-isomerism in the lanthanide series.

Oxidation of [(Ar-bian)Yb(dme)] (1) (Ar-bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene; dme = 1,2-dimethoxyethane) by 0.5 equivalent of MeNC(S)S-S(S)CNMe in dme at ambient temperature affords a mixture of two products, [(Ar-bian)Yb{SC(S)NMe}(dme)] and [(Ar-bian)Yb{SC(S)NMe}(dme)], which represent two redox-isomers (2a and 2b, respectively). Their ratio in solution depends on the solvent as well as on the temperature.

Specifics of Porous Polymer and Xenogeneic Matrices and of Bone Tissue Regeneration Related to Their Implantation into an Experimental Rabbit Defect.

This paper provides a study of two bone substitutes: a hybrid porous polymer and an osteoplastic matrix based on a bovine-derived xenograft. Both materials are porous, but their pore characteristics are different. The osteoplastic matrix has pores of 300-600 µm and the hybrid polymer has smaller pores, generally of 6-20 µm, but with some pores up to 100 µm across.

Ligand-Induced Intramolecular Redox Diversity in Titanium Complexes with Acenaphthene-1,2-diimine.

A series of the chlorido and alkoxychlorido titanium complexes of the general formula (dpp-Bian)Ti(OPr)Cl, where dpp-Bian = 1,2-bis[(2,6-PrCH)imino]acenaphthene = 0 (), 1 (), 2 (), as well as (dpp-Bian)Ti(OPr) () and (dpp-Bian)Ti(OPr)Cl (), were isolated and characterized using single-crystal X-ray diffraction analysis and spectroscopic studies combined with density functional theory (DFT) calculations. In the solid state, compounds reveal a square-pyramidal geometry at the metal center supported with monoanionic dpp-Bian, whereas with a neutral diimine ligand and bearing a dianionic enebisamide dpp-Bian show, respectively, an octahedral and tetrahedral coordination surrounding the metal ion. Paramagnetic complexes exhibit electron paramagnetic resonance spectra in both toluene solution and solid state, confirming the transfer of spin density from the metal ion to the dpp-Bian ligand as the number of alkoxy groups increases.

Diversity of transformation of heteroallenes on acenaphthene-1,2-diimine aluminum oxide.

The reactions of oxide [(dpp-bian)Al(μ-O)Al(dpp-bian)] (1) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with phenyl- or cyclohexylisocyanates result in the formation of carbonimidate derivatives [(dpp-bian)Al(μ-O)(μ-RNCO)Al(dpp-bian)] (R = Ph, 2; Cy, 3). Addition of ,'-dicyclohexylcarbodiimide to compound 1 leads to the formation of ureate complex [(dpp-bian)Al(μ-O)(μ-(CyN)CO)Al(dpp-bian)] (4). The reactions of the oxide 1 with pinacolborane and catecholborane afford oxo-bridged hydride [{(dpp-bian)Al(H)}(μ-O){Al(OBpin)(dpp-bian)}] (5) and compound [{(dpp-bian)Al(OBCat)}(μ-O)] (7), respectively.

Features of Changes in the Structure and Properties of a Porous Polymer Material with Antibacterial Activity during Biodegradation in an In Vitro Model.

Hybrid porous polymers based on poly-EGDMA and polylactide containing vancomycin, the concentration of which in the polymer varied by two orders of magnitude, were synthesized. The processes of polymer biodegradation and vancomycin release were studied in the following model media: phosphate-buffered saline (PBS), trypsin-Versene solution, and trypsin-PBS solution. The maximum antibiotic release was recorded during the first 3 h of extraction.

Effect of a single methyl substituent on the electronic structure of cobaltocene studied by computationally assisted MATI spectroscopy.

Metallocenes represent archetypical organometallic compounds playing key roles in various fields of fundamental and applied chemistry. Many of their unique properties arise from low ionization energies (IE) which can be tuned by introducing substituents into the rings. Here we report the first mass-analyzed threshold ionization (MATI) spectrum of a methylmetallocene, (Cp')(Cp)Co (Cp' = η-CHMe, Cp = η-CH).

Ca(II) and Yb(II) complexes featuring M(C≡C) structural motif: enforced proximity or genuine η -bonding?

Bis(carbazolide) complexes M[3,6-tBu -1,8-(RC≡C) Carb] (THF) (R=SiMe , n=0, M=Ca, Yb; R=Ph, n=1, M=Ca, Yb; n=0, M=Yb) were synthesized through transamination reaction of M[N(SiMe ) ] (THF) with two molar equivalents of carbazoles. The complexes feature M(η -C≡C) structural motif composed of M(II) ions encapsulated by four acetylene fragments due to atypical for alkaline- and rare-earth metals η -interactions with triple C≡C bond. This interaction is evidenced experimentally by X-ray diffraction, Raman spectroscopy in the solid state and by NMR-spectroscopy in the solution.

Cyanoarylporphyrazine dyes: multimodal compounds for personalised photodynamic therapy.

Photodynamic therapy is known as an effective primary and adjuvant anticancer treatment. Compounds with improved properties or additional modalities are still needed to create an 'ideal' photosensitizer. In this article, we review cyanoarylporphyrazine dyes for photodynamic (anticancer) therapy that we have synthesised to date.

Dendritic Cells Pulsed with Tumor Lysates Induced by Tetracyanotetra(aryl)porphyrazines-Based Photodynamic Therapy Effectively Trigger Anti-Tumor Immunity in an Orthotopic Mouse Glioma Model.

Research in the past decade on immunogenic cell death (ICD) has shown that the immunogenicity of dying tumor cells is crucial for effective anticancer therapy. ICD induction leads to the emission of specific damage-associated molecular patterns (DAMPs), which act as danger signals and as adjuvants to activate specific anti-tumor immune responses, leading to the elimination of tumor cells and the formation of long-term immunological memory. ICD can be triggered by many anticancer treatment modalities, including photodynamic therapy (PDT).

X/Y platinum(II) complexes: some features of supramolecular assembly halogen bonding.

Four series of new luminescent cyclometalated complexes [Pt(C^N)(IPy)Y] (HC^N = 2-phenylpyridine (Hppy), 2-(1-benzofuran-3-yl)pyridine (Hbfpy), methyl-2-phenylquinoline-4-carboxylate (Hmpqc), 2-(1-benzothiophen-3-yl)pyridine (Hbtpy), IPy = 4-iodopyridine, and Y = Cl, Br, I) have been investigated as X/Y 'building blocks' for the construction of a supramolecular network utilizing the I atom in IPy as a halogen bond (XB) donor (the X atom). The σ-hole of the X atom was found to provide non-covalent X⋯Y, X⋯Pt and X⋯π (π system of the metalated chelate ring) interactions for the complexes in the crystal state. NBO analysis confirms donation of the platinum electron density to iodine upon the X⋯Pt interaction.

Self-assembly of a metal-organic cage-like structure bearing cofacial redox-active bis-(-semiquinone) copper(II) units.

Ditopic di--quinone with a resorcinol bridge exhibits the ability to self-assemble in a reaction with copper, giving a cage-like binuclear complex that, due to the cofacially placed metal ions, is capable of encapsulation of different solvent molecules as guest ligands. Notably, the geometry of the internal cavity of this complex adjusts depending on the coordinating properties of the encapsulated molecule (mono- or bidentate). A feature of this species is that the cage-forming units are copper(II) bis-semiquinonate moieties, capable of undergoing ligand-centered redox transformations.

Lanthanide Coordination Polymers with Soft-Base Ditopic Bisthiazolate Ligands.

In order to prepare the first lanthanide coordination polymers (CPs) based on ditopic sulfide ligands, benzo[1,2-:4,5-']bisthiazole-2,6(3,7)-dithione (HL) was used as a linker. The reactions of lanthanide silylamides Ln[N(SiMe)] (Ln = Nd, Gd, Er, and Yb) with HL result in the formation of soluble dimethyl sulfoxide (DMSO) ionic salts [Ln(DMSO)][L] [Ln = Nd (), Gd (), Er (), and Yb ()]. Due to the lack of coordination of anionic ligands, compounds , , and do not show sensitized metal-centered photoluminescence (PL), while Gd compound shows weak phosphorescence at 77 K.

Pore Structure Tuning of Poly-EGDMA Biomedical Material by Varying the O-Quinone Photoinitiator.

Porous polymer monoliths with thicknesses of 2 and 4 mm were obtained via polymerization of ethylene glycol dimethacrylate (EGDMA) under the influence visible-light irradiation in the presence of a 70 wt% 1-butanol porogenic agent and o-quinone photoinitiators. The o-quinones used were: 3,5-di-tret-butyl-benzoquinone-1,2 (35Q), 3,6-di-tret-butyl-benzoquinone-1,2 (36Q), camphorquinone (CQ), and 9,10-phenanthrenequinone (PQ). Porous monoliths were also synthesized from the same mixture but using 2,2'-azo-bis(iso-butyronitrile) (AIBN) at 100 °C instead o-quinones.

Chemical and Electrochemical Reductions of Monoiminoacenaphthenes.

Redox properties of monoiminoacenaphthenes (MIANs) were studied using various electrochemical techniques. The potential values obtained were used for calculating the electrochemical gap value and corresponding frontier orbital difference energy. The first-peak-potential reduction of the MIANs was performed.

Porogen Concentration Effect on the Pore Structure and Properties Evolution of Polymer Monolith Based on Oligocarbonate Dimethacrylate OCM-2.

Porous polymer monolith materials of 2-mm thickness were obtained by visible light-induced radical polymerization of oligocarbonate dimethacrylate (OCM-2) in the presence of 1-butanol (10 to 70 wt %) as a porogenic additive. The pore characteristics and morphology of polymers were studied by mercury intrusion porosimetry and scanning electron microscopy. Monolithic polymers with both open and closed pores up to 100 nm in size are formed when the alcohol content in the initial composition is up to 20 wt %.

An investigation into the Brønsted acidity of the perfluorinated alkoxy silanes {(FC)CO}SiH and {(FC)CO}Si(Cl)H.

The perfluorinated alkoxy silanes {(FC)CO}SiH (1) and {(FC)CO}Si(Cl)H (2) were prepared and fully characterized. Despite the high calculated Brønsted acidities, all attempts to deprotonate 1 and 2 to give the conjugate silanide ions failed due to the exceptionally short and strong Si-H bonds. In the solid state, the Si-H units are not involved in any intermolecular interactions, but instead the crystal packing consists of exceptionally short and strong F⋯F interactions.