Dinuclear Rare-Earth β-Diketiminates with Bridging 3,5-Di-butyl-catecholates: Synthesis, Structure, and Single-Molecule Magnet Properties.

The dinuclear β-diketiminato complex [LClDy(μ-Cl)DyL(THF)] () (L = {2,6-PrCH-NC(Me)CHC(Me)N-2,6-PrCH}) was obtained by reaction of DyCl with KL in a molar ratio of 1:1 and used for the preparation of the mixed-ligand complex [LDy(μ-3,5-Cat)] () by salt metathesis reaction with 3,5-CatK (3,5-Cat -3,5-di--butyl-catecholate). Reactions of 3,5-CatNa with [LLnCl(THF)] (Ln = Dy, Y) ligated with the less bulky ligand L = {2,4,6-MeCH-NC(Me)CHC(Me)N-2,4,6-MeCH} afforded the mixed-ligand THF-containing complexes [LLn(μ-3,5-Cat)(THF)] (Ln = Dy (), Y ()). All new complexes were fully characterized, and the solid-state structures were determined by single-crystal X-ray diffraction.

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.

Solvent-controlled solid-state phase transitions of a heterospin Cu(II) complex with imidazolyl-substituted nitronyl nitroxide.

Spontaneous solvent-controlled solid-state transformations were observed for a series of polymeric chain solvates [Cu(hfac)L]·0.5Solv (Solv = (CH)CO, THF, CHCl, CHBr, CHCl) with 2-(1-propyl-1-imidazol-5-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1-imidazole-3-oxide-1-oxyl (L) under ambient conditions. The conversion of powdered polymeric chain [Cu(hfac)L]·0.

Pyridyl-Substituted Nitronyl Nitroxides: Comprehensive Magnetochemical and Quantum Chemical Study.

A series of pyridyl-substituted nitronyl nitroxides was synthesized and structurally characterized. A comprehensive magnetochemical and quantum chemical study of extended raw of the nitroxides with different substituents R in the pyridine fragment was performed. It was shown, that temperature-dependent magnetic properties are determined by the short contacts between nitroxide groups of adjacent molecules as well as between nitroxide group and methyl substituents in the pseudo axial positions of imidazoline fragments.

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.

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.

Hysteretic Room-Temperature Magnetic Bistability of the Crystalline 4,7-Difluoro-1,3,2-Benzodithiazolyl Radical.

The title radical R⋅, synthesized by reduction of the corresponding cation R, is thermally stable up to ~380 K in the crystalline state under anaerobic conditions. With SQUID magnetometry, single-crystal and powder XRD, solid-state EPR and TG-DSC, reversible spin-Peierls transition between diamagnetic and paramagnetic states featuring ~10 K hysteretic loop is observed for R⋅ in the temperature range ~310-325 K; ΔH=~2.03 kJ mol and ΔS=~6.

Ferrocenyl-substituted nitronyl nitroxide in the design of one-dimensional magnets.

By the reaction of M(hfac) (M = Mn(II), Co(II), Cu(II), and Zn(II); hfac is the hexafluoroacetylacetonate anion) and ferrocenyl-substituted nitronyl nitroxide (L), we succeeded in the synthesis of stable heterospin complexes: mononuclear [Zn(hfac)L], trinuclear {[Cu(hfac)]L} and chain polymer [Mn(hfac)L] and [Co(hfac)L]. The specific steric bulkiness of the ferrocenyl substituent leads to the formation of -type coordination polyhedra in the [Mn(hfac)L] and [Co(hfac)L] chains. The introduction of the ferrocene substituent leads to an effective weakening of intermolecular or interchain magnetic exchange coupling.

N-Alkylimidazol-5-yl-substituted Nitronyl Nitroxides and Their Mononuclear Cu(II) Complexes: Synthesis, Structure and Magnetic Properties.

A novel synthetic approach has been employed to synthesize a series of new nitronyl nitroxides: 2-(1-propyl-1H-imidazol-5-yl)- (L ), 2-(1-isopropyl-1H-imidazol-5-yl)- (L ) and 2-(1-butyl-1H-imidazol-5-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (L ). The reaction of Cu(hfac) with L in a 1 : 2 ratio yields mononuclear heterospin complexes [Cu(hfac) (L ) ] (L =L , L , L ), which have a similar crystal structure to the "jumping" crystals [Cu(hfac) (L ) ] that exhibit chemomechanical activity. It was shown that an increase in the alkyl substituent R leads to changes in the crystal packing of the molecules and the absence of chemomechanical activity.

Novel pyridyl-substituted nitronyl nitroxides as potential antiarrhythmic and hypotensive agents with low toxicity and enhanced stability in aqueous solutions.

This study explores the antiarrhythmic and hypotensive potential of pyridyl-substituted nitronyl nitroxides derivatives, uncovering the crucial role of a single carbon moiety of the pyridine cycle alongside radical and charged oxygen centers of the imidazoline fragment. Notably, the introduction of fluorine atoms diminished the antiarrhythmic effect, while the most potent derivatives featured the nitronyl nitroxide pattern positioned at the third site of the pyridine cycle. Gender-dependent responses were observed in lead compounds L and L, with L inducing temporary bradycardia and hypotension specifically in female rats, and L causing significant blood pressure reduction followed by rebound in females compared to milder effects in males.

A Nitronyl Nitroxide-Substituted Benzotriazinyl Tetraradical.

High-spin organic tetraradicals with significant intramolecular exchange interactions have high potential for advanced technological applications and fundamental research, but those synthesized to date possess limited stability and processability. In this work, we have designed a tetraradical based on the Blatter's radical and nitronyl nitroxide radical moieties and successfully synthesized it by using the palladium-catalyzed cross-coupling reaction of a triiodo-derivative of the 1,2,4-benzotriazinyl radical with gold(I) nitronyl nitroxide-2-ide complex in the presence of a newly developed efficient catalytic system. The molecular and crystal structure of the tetraradical was confirmed by X-ray diffraction analysis.

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.

New Ruthenium Nitrosyl Complexes Combining Potentially Photoactive Nitrosyl Group with the Magnetic Nitroxide Radicals as Ligands.

Two ruthenium nitrosyl complexes of Na[RuNOClL] with nitronyl nitroxide radicals coordinated to ruthenium with N-donor pyridine rings were prepared and described. The crystal structure of both complexes is 1D or 2D polymeric, due to the additional coordination of sodium cation by bridging the chloride ligands or oxygen atoms of nitroxides. Partially, the oligomeric forms remain in the solutions of the complexes in acetonitrile.

High-field EPR of copper(II)-nitroxide compound exhibiting three-step phase transition: structural insights from the field-induced sample orientation.

Copper(II)-nitroxide based Cu(hfac)L compounds exhibit unusual magnetic behavior that can be induced by various stimuli. In many aspects, the magnetic phenomena observed in Cu(hfac)L are similar to classical spin-crossover behavior. However, these phenomena originate from polynuclear exchange-coupled spin clusters Cu-O˙-N< or >N-˙O-Cu-O˙-N<.

Perfluoroalkyl Chain Length Effect on Crystal Packing and [LnO] Coordination Geometry in Lanthanide-Lithium β-Diketonates: Luminescence and Single-Ion Magnet Behavior.

Functionalized perfluoroalkyl lithium β-diketonates (LiL) react with lanthanide(III) salts (Ln = Eu, Gd, Tb, Dy) in methanol to give heterobimetallic Ln-Li complexes of general formula [(LnL)(LiL)(MeOH)]. The length of fluoroalkyl substituent in ligand was found to affect the crystal packing of complexes. Photoluminescent and magnetic properties of heterobimetallic β-diketonates in the solid state are reported.

Cobalt(II) coordination to an N-acenaphthene-based ligand and its sodium complex.

A new bifunctional N-ligand was obtained the condensation reaction of acenaphthenequinone and 2-picolylamine. A peculiarity of this synthesis is the formation of a new intramolecular C-C bond during the reaction. The structure and redox properties of the ligand were studied.

Synthesis, crystal polymorphism and spin crossover behavior of adamantylboron-capped cobalt(II) hexachloroclathrochelate and its transformation into the CoCoCo-bis-macrobicyclic derivative.

Fast crystallization of the monoclathrochelate cobalt(II) intracomplex [Co(ClGm)(BAd)] (where ClGm is a dichloroglyoxime dianion and BAd is an adamantylboron capping group, 1), initially obtained by the direct template condensation of the corresponding chelating α-dioximate and cross-linking ligand synthons on the Co ion as a matrix, from benzene or dichloromethane afforded its structural triclinic and hexagonal polymorphs. Its prolonged recrystallization from dichloromethane under air atmosphere and sunlight irradiation unexpectedly gave the crystals of the CoCoCo-trinuclear dodecachloro-bis-clathrochelate intracomplex [[Co(ClGm)(BAd)]Co] (2), the molecule of which consists of two macrobicyclic frameworks with encapsulated low-spin (LS) Co ions, which are cross-linked by a μ-bridging Co ion as a bifunctional Lewis-acidic center. The most plausible pathway of such a 1 → 2 transformation is based on the photoinitiated radical oxidation of dichloromethane with air oxygen giving the reactive species.

Charge Transfer Chromophores Derived from 3d-Row Transition Metal Complexes.

A series of new charge transfer (CT) chromophores of "α-diimine-M-catecholate" type (where M is 3d-row transition metals-Cu, Ni, Co) were derived from 4,4'-di--butyl-2,2'-bipyridyl and 3,6-di--butyl--benzoquinone () in accordance with three modified synthetic approaches, which provide high yields of products. A square-planar molecular structure is inherent for monomeric () and () chromophores, while dimeric complex () units two substantially distorted heteroleptic D-M-A (where D, M, A are donor, metal and acceptor, respectively) parts through a donation of oxygen atoms from catecholate dianions. Chromophores - undergo an effective photoinduced intramolecular charge transfer (λ = 500-715 nm, extinction coefficient up to 10 M·cm) with a concomitant generation of a less polar excited species, the energy of which is a finely sensitive towards solvent polarity, ensuring a pronounced negative solvatochromic effect.

Ferromagnetic Layers in a Topological Insulator (Bi,Sb)Te Crystal Doped with Mn.

Magnetic topological insulators (MTIs) have recently become a subject of poignant interest; among them, Z topological insulators with magnetic moment ordering caused by embedded magnetic atoms attract special attention. In such systems, the case of magnetic anisotropy perpendicular to the surface that holds a topologically nontrivial surface state is the most intriguing one. Such materials demonstrate the quantum anomalous Hall effect, which manifests itself as chiral edge conduction channels that can be manipulated by switching the polarization of magnetic domains.

2-Imidazoline Nitroxide Derivatives of Cymantrene.

The 2-imidazoline nitroxide derivatives of cymantrene-2-(-cyclopentadienyl)tricarbonylmanganese(I)-4,4,5,5-tetramethyl-4,5-dihydro-1-imidazole-3-oxide-1-oxyl (NNMn) and 2-(-cyclopentadienyl)tricarbonylmanganese(I)-4,4,5,5-tetramethyl-4,5-dihydro-1-imidazole-1-oxyl (INMn) were synthesized. It was shown that NNMn and INMn exhibit a sufficiently high kinetic stability both in solids and in solutions under normal conditions. Their structural characteristics, magnetic properties and electrochemical behavior are close to Re(I) analogs.

Re(i)-nitroxide complexes.

Spin-labeled cyrhetrenes [(NNCp)Re(CO)] and [(INCp)Re(CO)], where NNCp is nitronyl nitroxide 2-(η-cyclopentadienyl)-4,4,5,5-tetramethyl-4,5-dihydro-1-imidazole-3-oxide-1-oxyl and INCp is the corresponding imino nitroxide, were synthesized and characterized by EPR, CV, XRD, magnetochemistry and quantum chemistry methods. The correlations between different arrangements of paramagnetic centers and the magnetic exchange interactions for three polymorphs of [(NNCp)Re(CO)] were studied. It was concluded that high kinetic stability of nitroxide-substituted cyrhetrenes is a promising feature of compounds for the creation of multifunctional contrast agents.

Platform for High-Spin Molecules: A Verdazyl-Nitronyl Nitroxide Triradical with Quartet Ground State.

Thermally resistant air-stable organic triradicals with a quartet ground state and a large energy gap between spin states are still unique compounds. In this work, we succeeded to design and prepare the first highly stable triradical, consisting of oxoverdazyl and nitronyl nitroxide radical fragments, with a quartet ground state. The triradical and its diradical precursor were synthesized via a palladium-catalyzed cross-coupling reaction of diiodoverdazyl with nitronyl nitroxide-2-ide gold(I) complex.

Versatile Reactivity of Mn Complexes in Reactions with N-Donor Heterocycles: Metamorphosis of Labile Homometallic Pivalates vs. Assembling of Endurable Heterometallic Acetates.

Reaction of 2,2'-bipyridine (2,2'-bipy) or 1,10-phenantroline (phen) with [Mn(Piv)(EtOH)] led to the formation of binuclear complexes [Mn(Piv)L] (L = 2,2'-bipy (), phen (); Piv is the anion of pivalic acid). Oxidation of or by air oxygen resulted in the formation of tetranuclear Mn complexes [MnO(Piv)L] (L = 2,2'-bipy (), phen ()). The hexanuclear complex [Mn(OH)(Piv)(pym)] () was formed in the reaction of [Mn(Piv)(EtOH)] with pyrimidine (pym), while oxidation of produced the coordination polymer [MnO(Piv)(pym)] ().

Metal-Organic Frameworks Derived from Calcium and Strontium Complexes of a Redox-Active Ligand.

The reactions of monomeric [(dpp-Bian)M(thf)] (M = Ca (), Sr (); dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with 4,4'-bipyridyl (4,4'-bipy) proceed with electron transfer from dpp-Bian to 4,4'-bipy to afford calcium and strontium complexes containing simultaneously radical-anionic dpp-Bian and 4,4'-bipy ligands. In tetrahydrofuran (thf) the reactions result in 1D coordination polymers [{(dpp-Bian)M(4,4'-bipy)(thf)}·4thf] (M = Ca (), Sr ()), while in a thf/benzene mixture the reaction between and 4,4'-bipy affords the 2D metal-organic framework [{(dpp-Bian)Ca(4,4'-bipy)}·2thf·2CH] (). The structures of compounds , and have been determined by single-crystal X-ray analyses.