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.

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.

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 .

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.

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.

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).

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.

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.

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 %.

Reactions of Low-Valent Gallium Species with Organic Azides: Formation of Imido-, Azoimido-, and Tetrazene Complexes.

The reactivity of two α-diimine-ligated digallanes, [LGa-GaL] (L = [(2,6-iPrCH)NC(CH)], dpp-dad, ; L = 1,2-[(2,6-iPrCH)NC]CH, dpp-bian, ), and a gallylene, [(L)GaNa(THF)] (), toward organic azides was studied. Reaction of digallane or with trimethylsilyl azide (MeSiN), 2-azido-benzonitrile (2-CNCHN), or tosylazide (TosN) results in imido-bridged complexes, [(L)Ga(μ-NSiMe)Ga(L)] () [(L)Ga(μ-NSiMe)Ga(L)] (), [(L)Ga(μ-2-CNCHN)Ga(L)] (), and [(L)Ga(μ-NTos)Ga(L)] (), with elimination of dinitrogen. Treatment of or with 1-adamantyl azide (1-AdN), on the other hand, affords the unsymmetrical dinuclear complexes [(L)Ga(NAd)(NAd)Ga(L)] () and [(L)Ga(NAd)(NAd)Ga(L)] (), which contain both imido and triazene bridges.

Novel Rigidochromic and Anti-Kasha Dual Emission Fluorophores Based on D-π-A Dyads as the Promising Materials for Potential Applications Ranging from Optoelectronics and Optical Sensing to Biophotonics and Medicine.

Today we see an increasing demand for new fluorescent materials exhibiting various sensory abilities due to their broad applicability ranging from the construction of flexible devices to bioimaging. In this paper, we report on the new fluorescent pigments AntTCNE, PyrTCNE, and PerTCNE which consist of 3-5 fused aromatic rings substituted with tricyanoethylene fragments forming D-π-A diad. Our studies reveal that all three compounds exhibit pronounced rigidochromic properties, i.

Synthesis and Antimicrobial Activity of Sulfenimines Based on Pinane Hydroxythiols.

The widespread presence of multidrug-resistant pathogenic microorganisms challenges the development of novel chemotype antimicrobials, insensitive to microbial tools of resistance. To date, various monoterpenoids have been shown as potential antimicrobials. Among many classes of molecules with antimicrobial activity, terpenes and terpenoids are an attractive basis for the design of antimicrobials because of their low toxicity and availability for various modifications.

Synthesis of Trifluoromethylated Monoterpene Amino Alcohols.

For the first time, monoterpene trifluoromethylated β-hydroxy-benzyl--oximes were synthesized in 81-95% yields by nucleophilic addition of the Ruppert-Prakash reagent (TMSCF) to the corresponding β-keto-benzyl--oximes based on (+)-nopinone, (-)-verbanone and (+)-camphoroquinone. Trifluoromethylation has been determined to entirely proceed chemo- and stereoselective at the C=O rather than C=N bond. Trifluoromethylated benzyl--oximes were reduced to the corresponding α-trifluoromethyl-β-amino alcohols in 82-88% yields.

Ionization of Decamethylmanganocene: Insights from the DFT-Assisted Laser Spectroscopy.

Metallocenes represent one of the most important classes of organometallics with wide prospects for practical use in various fields of chemistry, materials science, molecular electronics, and biomedicine. Many applications of these metal complexes are based on their ability to form molecular ions. We report the first results concerning the changes in the molecular and electronic structure of decamethylmanganocene, Cp*Mn, upon ionization provided by the high-resolution mass-analyzed threshold ionization (MATI) spectroscopy supported by DFT calculations.

Reactivity of Transition Metal Gallylene Complexes Toward Substrates with Multiple Carbon-Element Bonds.

Reactivity of transition metal complexes containing the redox-active gallylene (dpp-bian)Ga ligand (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) toward isocyanide, isocyanate, isothiocyanate, and ketene substrates is described. The reaction of [(dpp-bian)GaCr(CO)] () with tBuNC results in a dative complex [(dpp-bian)Ga(CNtBu)Cr(CO)] (), while compound [(dpp-bian)GaCr(CO)][Na(THF)] () reacts with tBuNC to give the coordination polymer [(dpp-bian)GaCr(CO)][Na(CNtBu)(THF)] (). Treatment of [(dpp-bian)GaCr(CO)][Na(THF)] with an excess of PhNCO results in trimerization of the latter and formation of complex [(dpp-bian)GaCr(CO)][Na(PhNCO)(EtO) (DME)] ().

π-Carbazolyl supported bis(alkyl) complexes of Sc, Y and La for α-olefin polymerization and hydrogenation.

A series of new half-sandwich bis(alkyl) rare-earth metal complexes coordinated by a sterically demanding 1,3,6,8-tetra--butyl-carbazol-9-yl ligand [BuCarb]La(CHCH)(THF) (1-La), [BuCarb]Ln(-NMeCHCH) (Ln = Sc (2-Sc), Y (2-Y), La (2-La), [BuCarb]Ln(CHSiMe)(THF) (Ln = Sc (3-Sc), Y (3-Y)), were synthesized. 1-La, 2-La, and 2-Y were prepared by an alkane elimination protocol, while 2-Sc, 3-Sc, and 3-Y became accessible only when salt metathesis reactions of BuCarbK with RLn(THF)[BPh] were employed. X-ray analysis revealed that in all complexes the carbazolyl ligand exhibits π-coordination with metal ions.

Unraveling of Functional Activity of Primary Hippocampal Neuron-Glial Networks in Photodynamic Therapy Based on Tetracyanotetra(aryl)porphyrazines.

The current efforts in photodynamic therapy (PDT) of brain cancer are focused on the development of novel photosensitizers with improved photodynamic properties, targeted specific localization, and sensitivity to the irradiation dose, ensuring the effectiveness of PDT with fewer side effects for normal nerve tissue. Here, we characterize the effects of four photosensitizers of the tetracyanotetra(aryl)porphyrazine group (-) on the functional activity of neuron-glial networks in primary hippocampal cultures in their application in normal conditions and under PDT. The data revealed that the application of - leads to a significant decrease in the main parameters of the functional calcium activity of neuron-glial networks and pronounced changes in the network characteristics.

Cycloaddition of isoselenocyanates to sodium and magnesium metallacycles.

Heterocumulenes SeCNR (R = CHOMe-2, CHMe-2) undergo facile cycloaddition to [(H-dpp-bian)Na(EtO)] (1) (H-dpp-bian = N-protonated 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) resulting in cycloadducts [(H-dpp-bian)Na(SeCNR)(DME)] (2, 3), which are the first cycloadducts derived from a sodium metallacycle reported so far. A comparative reaction of [(dpp-bian)Mg(THF)] (10) with SeCNR gives magnesium cycloadducts [(dpp-bian)Mg(SeCNR)(Solv)] (11, 12), which undergo fast decomposition at room temperature. New compounds are characterized by NMR, EPR, and IR spectroscopy, and elemental and X-ray diffraction analysis.