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.

Macrocyclic Bridgehead Fluorophores, Pyrrolyl-diazabicyclo[8.3.1]tetradecadienones, with Giant Stokes Shifts.

A previously unknown class of fluorophores was discovered, which represents 14-membered bridgehead heterocycles, pyrrolyl-diazabicyclo[8.3.1]tetradecadienones, herein referred to as PY-14-ONEs.

Enhancing Photostability of Complex Lead Halides through Modification with Antibacterial Drug Octenidine.

The high power-conversion efficiencies of hybrid perovskite solar cells encourage many researchers. However, their limited photostability represents a serious obstacle to the commercialization of this promising technology. Herein, we present an efficient method for improving the intrinsic photostability of a series of commonly used perovskite material formulations such as MAPbI, FAPbI, CsFAPbI, and CsMAFAPbI through modification with octenidine dihydroiodide (), which is a widely used antibacterial drug with two substituted pyridyl groups and two cationic centers in its molecular framework.

Spin polarization effects in trigonal mixed-valence complexes exhibiting double exchange supported by external spin-cores.

The theory of the magnetic coupling between the localized spins, mediated by the mobile excess electron, is generalized to the case of a trigonal, six-center, four-electron molecule with partial valence delocalization. The combination of the electron transfer occurring within the valence-delocalized subsystem and the interatomic exchange producing coupling of the spin of the mobile electron of valence-delocalized fragment with the three localized spins forming the valence-localized subsystem leads to the appearance of a special kind of double exchange (DE), termed the "external core double exchange" (ECDE), in order to distinguish such DE from the conventional "internal core double exchange" for which the mobile electron is coupled with the spin-cores on the same center via the intra-atomic exchange. The effect of the ECDE on the ground spin state of the considered trigonal molecule is compared with earlier reported effect produced by DE in the four-electron, mixed-valence (MV) trimer.

Magnetically bistable cobalt-dioxolene complexes with a tetradentate N-donor base.

Synthesis and magnetic characterization of a family of cobalt-dioxolene complexes [(MeTPA)Co(36-DBCat)] (1), [(MeTPA)Co(36-DBCat)](PF) (2) and [(MeTPA)Co(diox-(OMe))](BPh) (3) (MeTPA = bis(6-methyl-2-pyridyl)methyl-(2-pyridylmethyl)amine; 36-DBCat = dianion of 3,6-di--butylcatechol; diox-(OMe) - 2,5-di--butyl-3,3,4-trimethoxy-6-oxocyclohexa-1,4-dienolate) is reported. The neutral complex 1 is found to form hexa- (CoON, 1a) and pentacoordinated (CoON, 1b) isomers. Variable temperature single crystal X-ray diffraction analysis of 1a and 1b clearly indicates the presence of the high-spin divalent metal ion and the dianionic catecholate form of the dioxolene ligand.

Spin-Crossover and Slow Magnetic Relaxation Behavior in Hexachlororhenate(IV) Salts of Mn(III) Complexes [Mn(5-Hal-sal323)][ReCl] (Hal = Cl, Br).

The cationic complexes of Mn(III) with the 5-Hal-sal323 (Hal = Cl, Br) ligands and a paramagnetic doubly charged counterion [ReCl] have been synthesized: [Mn(5-Cl-sal323)][ReCl] () and [Mn(5-Br-sal323)][ReCl] (). Their crystal structures and magnetic properties have been studied. These isostructural two-component ionic compounds show a thermally induced spin transition at high temperature associated with the cationic subsystem and a field-induced slow magnetic relaxation of magnetization at cryogenic temperature, associated with the anionic subsystem.

Quintet Dinitrenes with Negative Zero-Field Splitting: Effect of Spin-Orbit Coupling on the Sign of Magnetic Anisotropy.

We report on W-band EPR and quantum chemical investigation of novel organic tetraradicals with negative axial zero-field splitting (ZFS) parameter These belong to the class of quintet 1,3,5-tribromophenylene-2,4-dinitrenes bearing different substituents in position 6 of the benzene ring (, N; , F; , CN; ; Cl; , Br). Analysis of the W-band EPR spectrum of dinitrene reveals its large negative ZFS parameter = -0.27 cm.

Vibronic recovering of functionality of quantum cellular automata based on bi-dimeric square cells with violated condition of strong Coulomb repulsion.

Strong Coulomb repulsion between the two charges in a square planar mixed-valence cell in quantum cellular automata (QCA) allows us to encode the binary information in the two energetically beneficial diagonal distributions of the electronic density. In this article, we pose a question: to what extent is this condition obligatory for the design of the molecular cell? To answer this question, we examine the ability to use a square-planar cell composed of one-electron mixed valence dimers to function in QCA in a general case when the intracell Coulomb interaction U is not supposed to be extremely strong, which means that it is comparable with the characteristic electron transfer energy (violated strong U limit). Using the two-mode vibronic model treated within the semiclassical (adiabatic) and quantum-mechanical approaches, we demonstrate that strong vibronic coupling is able to create a considerable barrier between the two diagonal-type charge configurations, thus ensuring bistability and polarizability of the cells even if the Coulomb barrier is not sufficient.

Evidence for zero-field slow magnetic relaxation in a Co(II) complex with a pseudo-tetrahedral NI environment.

Herein, we report on the synthesis, structure and magnetic properties of a four-coordinate mononuclear Co(II) diiodide complex with the 3,5-dimethylpyrazole ligand. A distorted tetrahedral local coordination environment around the central cobalt ion is formed by the two nitrogen atoms of two monodentate pyrazole ligands and by iodide ions. Direct current (dc) magnetic measurements in combination with SA-CASSCF/NEVPT2 quantum-chemical calculations revealed a strong easy-axis-type magnetic anisotropy with a record value = -30.

The powder X-band electron paramagnetic resonance spectroscopy of septet pyridyl-2,4,6-trinitrene.

The first X-band EPR spectrum containing only non-overlapping signals of septet pyridyl-2,4,6-trinitrene and triplet pyridylnitrenes is reported. This spectrum was recorded after photolysis of 2,4,6-triazidopyridine in solid argon at 5 K. The zero-field splitting (ZFS) parameters of this trinitrene as well as of intermediate triplet mononitrenes and quintet dinitrenes formed at early stages of the photolysis were determined using the combination of modern computer line-shape spectral simulations and density functional theory (DFT) calculations.

Nanoscale Visualization of Photodegradation Dynamics of MAPbI Perovskite Films.

Herein, we report the nanoscale visualization of the photochemical degradation dynamics of MAPbI (MA = CHNH) using infrared scattering scanning near-field microscopy (IR s-SNOM) combined with a series of complementary analytical techniques such as UV-vis and FTIR-spectroscopy, XRD, and XPS. Light exposure of the MAPbI films resulted in a gradual loss of MA cations starting from the grain boundaries at the film surface and slowly progressing toward the center of the grains and deeper into the bulk perovskite phase. The binary lead iodide PbI was found to be the major perovskite photochemical degradation product under the experimental conditions used.

Magnetic behavior of the novel pentagonal-bipyramidal erbium(III) complex (EtNH)[Er(HDAPS)Cl]: high-frequency EPR study and crystal-field analysis.

We report the synthesis, crystal structure and magnetic properties of the new heptacoordinated mononuclear erbium(III) complex (EtNH)[Er(HDAPS)Cl] (HDAPS = 2,6-diacetylpyridine bis-(salicylhydrazone)) (1). The coordination polyhedron around the Er(III) ion features a slightly distorted pentagonal bipyramid formed by the pentagonal NO chelate ring of the HDAPS ligand in the equatorial plane and two apical chloride ligands. Detailed high-frequency/high-field electron paramagnetic resonance (HF-EPR) studies of 1 result in the precise determination of the crystal field (CF) splitting energies (0, 290 and 460 GHz) and effective -values of the three lowest Kramers doublets (KDs) of the Er(III) ion.

A Series of Novel Pentagonal-Bipyramidal Erbium(III) Complexes with Acyclic Chelating Schiff-Base Ligands: Synthesis, Structure, and Magnetism.

A series of six seven-coordinate pentagonal-bipyramidal (PBP) erbium complexes, with acyclic pentadentate [] Schiff-base ligands, 2,6-diacetylpyridine bis-(4-methoxybenzoylhydrazone) [HDAPMBH], or 2,6-diacethylpyridine bis(salicylhydrazone) [HDAPS], and various apical ligands in different charge states were synthesized: [Er(DAPMBH)(CHOH)Cl] (); [Er(DAPMBH)(HO)Cl]·2CHOH (); [Er(DAPMBH)(CHOH)Cl] (); [Er(DAPMBH)(CHOH)(N)] (); [(EtH)N][Er(HDAPS)Cl] (); and [(EtH)N][Y.Er.(HDAPS)Cl] ().

Abrupt Spin-State Switching in Mn(III) Complexes with BPh Anion: Effect of Halide Substituents on Crystal Structure and Magnetic Properties.

Three tetraphenylborates of mononuclear Mn(III) cation complexes with hexadentate ligands, the products of the reaction between a N,N'-bis(3-aminopropyl)ethylenediamine and salicylaldehydes with the different haloid substitutions at the 5 or 3,5 positions, have been synthesized: [Mn(5-F-sal-N-1,5,8,12)]BPh (1), [Mn(3,5-diCl-sal-N-1,5,8,12)]BPh (2) and [Mn(3,5-Br,Cl-sal-N-1,5,8,12)]BPh (3). Their crystal structure, dielectric constant (ϵ) and magnetic properties have been studied. Ligand substituents have a dramatic effect on the structure and magnetic properties of the complexes.

Field-induced single-ion magnet based on a quasi-octahedral Co(II) complex with mixed sulfur-oxygen coordination environment.

Synthesis and characterization of structure and magnetic properties of the quasi-octahedral complex (pipH)[Co(TDA)] 2HO (I), (pipH = piperazine dication, TDA = thiodiacetic anion) are described. X-ray diffraction studies reveal the first coordination sphere of the Co(II) ion, consisting of two chelating tridentate TDA ligands with a mixed sulfur-oxygen strongly elongated octahedral coordination environment. SQUID magnetometry, frequency-domain Fourier-transform (FD-FT) THz-EPR spectroscopy, and high-level SA-CASSCF/NEVPT2 quantum chemical calculations reveal a strong "easy-plane" type magnetic anisotropy ( ≈ +54 cm) of complex I.

Insight Into The Spin-Vibronic Problem of a Mixed Valence Magnetic Molecular Cell for Quantum Cellular Automata.

The effects of the vibronic coupling in quantum cellular automata (QCA) based on the square planar mixed valence (MV) molecular cells comprising four paramagnetic centers (spin cores) and two excess mobile electrons are analyzed in the important particular case when the Coulomb energy gap between the ground antipodal diagonal-type two-electron configurations and the excited side-type configurations considerably exceeds both the one-electron transfer parameter (strong U-limit) and the vibronic stabilization energy. Under such conditions the developed model involves the second-order double exchange, the Heisenberg-Dirac-Van Vleck (HDVV) exchange and the vibronic coupling of the excess electrons with the molecular B -vibration composed of four full-symmetric local vibrations. The latter interaction is shown to significant amplify the ability of the electric field produced by the driver-cell to polarize the excess electrons in the working cell, which can be termed "the effect of the vibronic enhancement of the cell-cell interaction".

Generation and direct EPR spectroscopic observation of triplet arylphosphinidenes: stabilisation internal rearrangements.

Triplet phosphinidenes, which have been postulated as important intermediates in numerous organophosphorus reactions, have been previously directly observed only in isolated cases. Recently we have published the first recorded EPR spectrum of triplet phosphinidene-mesitylphosphinidene (A. V.

Field-induced SIM behaviour of a Co(II) complex with a 1,1'-diacetylferrocene-derived ligand.

Herein, we report the synthesis and magnetic properties of the Co(ii) coordination compound with the 1,1'-bis(1-((pyrid-2-ylmethylene)hydrazono)ethyl)ferrocene (L) ligand, having the general formula [CoLCl2]. The static magnetic data analysis supported by the CASSCF/NEVPT2 calculations revealed the presence of the triaxial magnetic anisotropy with Dexp = +35.2 cm-1 and large rhombicity (E/D = 0.

Complexes of Cobalt(II) Iodide with Pyridine and Redox Active 1,2-Bis(arylimino)acenaphthene: Synthesis, Structure, Electrochemical, and Single Ion Magnet Properties.

Complexes [(dpp-BIAN)CoI]·MeCN () and [(Py)CoI] () were synthesized by the reaction between cobalt(II) iodide and 1,2-bis(2,6-diisopropylphenylimino)acenaphthene (dpp-BIAN) or pyridine (Py), respectively. The molecular structures of the complexes were determined by X-ray diffraction. The Co(II) ions in both compounds are in a distorted tetrahedral environment (CoNI).

Purely Spectroscopic Determination of the Spin Hamiltonian Parameters in High-Spin Six-Coordinated Cobalt(II) Complexes with Large Zero-Field Splitting.

Accurate determination of the spin Hamiltonian parameters in transition-metal complexes with large zero-field splitting (ZFS) is an actual challenge in studying magnetic and spectroscopic properties of high-spin transition metal complexes. Recent critical papers have convincingly shown that previous determinations of these parameters, based only on the magnetic data, have low accuracy and reliability. A combination of X-band electron paramagnetic resonance (EPR) spectroscopy and SQUID magnetometry seems to be a more convincing and accurate approach.

The First Conducting Spin-Crossover Compound Combining a Mn Cation Complex with Electroactive TCNQ Demonstrating an Abrupt Spin Transition with a Hysteresis of 50 K.

We present herein the synthesis, crystal structure, and electric and magnetic properties of the spin-crossover salt [Mn(5-Cl-sal-N-1,5,8,12)]TCNQ ⋅2 CH CN (I), where 5-Cl-sal-N-1,5,8,12=N,N'-bis(3-(2-oxy-5-chlorobenzylideneamino)propyl)-ethylenediamine, containing distinct conductive and magnetic blocks along with acetonitrile solvent molecules. The Mn complex with a Schiff-base ligand, [Mn(5-Cl-sal-N-1,5,8,12)] , acts as the magnetic unit, and the π-electron acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ ) is the conducting unit. The title compound (I) exhibits semiconducting behavior with room temperature conductivity σ ≈1×10  ohm  cm and activation energy Δ ≈0.

Field-induced single-ion magnet behaviour of a hexacoordinated Co(ii) complex with easy-axis-type magnetic anisotropy.

A coordination compound with the composition [CoLCl2]·H2O (L = bis-condensation product of diacetyl and 2-hydrazinyl-4,6-dimethylpyrimidine) was synthesized, in which the Co(ii) ion was hexacoordinated. Under applied DC fields, this compound exhibited single-ion magnet behavior. Two relaxation processes were observed when increasing the applied magnetic field from 1000 to 3200 Oe.

EPR spectroscopy of multicomponent, multispin molecular system obtained by the photolysis of 2,4,6-triazido-3-cyano-5-fluoropyridine in solid argon.

Complex multicomponent, multispin molecular system, consisting of a septet trinitrene, two quintet dinitrenes, and three triplet mononitrenes, was obtained by the photolysis of 2,4,6-triazido-3-cyano-5-fluoropyridine in solid argon. To identify these paramagnetic products, electron paramagnetic resonance spectroscopy in combination with line-shape spectral simulations and density functional theory calculations was used. The products of the photolysis was found to be triplet 2,4-diazido-3-cyano-5-fluoropyridyl-6-nitrene (D  = 1.

Steric Heavy Atom Effect on Magnetic Anisotropy of Triplet Tribromophenyl Nitrenes.

Previously unknown the steric heavy atom effect on magnetic anisotropy parameters of triplet phenyl nitrenes is reported. The heavy bromine atom effect is revealed by W-band EPR and theoretical investigations of triplet 2,4,6-tribromophenyl nitrenes bearing different substituents in positions 3 and 5 of the phenyl ring (1a, H/H; 1b, CN/CN; 1c, N/F; 1d, N/N; 1e, Cl/Cl; 1f, Br/Br). The zero-field splitting parameters of nitrenes 1a ( D = 0.

Evidence of field induced slow magnetic relaxation in cis-[Co(hfac)(HO)] exhibiting tri-axial anisotropy with a negative axial component.

We report a combined experimental characterization and theoretical modeling of the hexa-coordinated high-spin Co(ii) complex cis-[Co(hfac)(HO)] (I). The magnetic static field (DC) data and EPR spectra (measurements were carried out on the powder samples of diluted samples cis-[CoZn (hfac)(HO)]) were analyzed with the aid of the parametric Griffith Hamiltonian for the high-spin Co(ii) supported by the ab initio calculations of the crystal field (CF) parameters, g-factors and superexchange parameters between H-bonded Co(ii) ions in the neighboring molecules in a 1D network. This analysis suggests the presence of the easy axis of magnetic anisotropy and also shows the existence of a significant rhombic component.