Design of luminescent complexes with different CuI cores based on pyridyl phenoxarsines.

A series of luminescent CuI clusters with stair-step, cubane, and octahedral geometries supported by a novel type of cyclic As,N-ligand, pyridyl-containing 10-phenoxarsines, were synthesized and characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction analysis. An unusual arrangement of As,N-bidentate and μ-iodo ligands was found in the octahedral cluster. The structural diversity of the Cu(I) complexes is reflected in their photophysical properties: the phosphorescence spectra of the compounds display emission in a broad spectral range of 495-597 nm.

PNP Ligands in Cobalt-Mediated Activation and Functionalization of White Phosphorus.

Transition-metal mediated white phosphorus activation is of high interest as an ecological alternative to P chlorination pathway to the practically useful phosphorus products. Herein, we report a facile approach for P activation, transformation and subsequent functionalization using cobalt complexes bearing PNP ligands. The use of N,N-bis(diphenylphosphino)amine as a ligand allows one to transform P tetrahedron into a zig-zag chain with the formation of complex [Co(Ph PNHP(Ph )PPPPP(Ph )NHPPh )]BF (4).

Dendritic Iron(III) Carbazole Complexes: Structural, Optical, and Magnetic Characteristics.

This paper focuses on the synthesis, structural characterization, and study of the optical, magnetic, and thermal properties of novel architectures combining metal ions as magnetoactive centers and photoactive blocks formed by carbazole units. For this purpose, a series of azomethine complexes of the composition [Fe(L)]X (L = 3,6-bis[(3',6'-di--butyl-9-carbazol)-9-carbazol]benzoyloxy-4-salicylidene-N'-ethyl-N-ethylenediamine, X = NO, Cl, PF) were synthesized by the reaction of metal salts with Schiff bases in a mixture of solvents. The UV-Vis absorption properties were studied in dichloromethane and rationalized via time-dependent density functional theory (DFT) calculations.

Luminescent CuI-cubane clusters based on -methyl-5,10-dihydrophenarsazines.

Two luminescent CuI-cubane tetramers with -methyl-10-(-halogenophenyl)-5,10-dihydrophenarsazine ligands were synthesized and characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction analysis. The UV-Vis absorption and emission properties were studied and rationalized by DFT and time-dependent DFT calculations. The luminescence behavior was found to be rather different from that of recently reported tetranuclear copper iodide cubane clusters based on As,O-analogues - 10-(aryl)phenoxarsines.

Platinum(II) Complexes with 10-(Aryl)phenoxarsines: Synthesis, Cis/Trans Isomerization, and Luminescence.

Synthesis and structural and photophysical characterization of platinum dihalogenide complexes formulated as [PtHalL], where Hal = Cl and I, with different 10-(aryl)phenoxarsine ligands such as 10-(-chlorophenyl)phenoxarsine, 10-(-tolyl)phenoxarsine, and 10-(phenyl)phenoxarsine are reported. The structures of complexes were determined by NMR spectroscopy, mass spectrometry, and X-ray analysis. Cis/trans isomerism of the complexes in solution was studied by NMR spectroscopy.

A new heterometallic pivalate {FeCd} complex as an example of unusual "ferric wheel" molecular self-assembly.

The interaction of the pivalate complexes of iron(iii), [Fe3O(Piv)6(H2O)3]·HPiv, and cadmium(ii), [Cd(Piv)2], in Et2O resulted in one more type of "ferric wheel" family complex, namely [Fe8(Piv)16{Cd(Piv)2}(μ-OH)8]·Et2O (1). The complex is an octanuclear iron(iii) wheel with a {Cd(Piv)2} moiety asymmetrically incorporated into the ring.

(Pyrrole-2,5-Diyl)-Bis(Nitronyl Nitroxide) and-Bis(Iminonitroxide): Specific Features of the Synthesis, Structure, and Magnetic Properties.

In contrast to diradicals connected by alternant hydrocarbons, only a few studies have addressed diradicals connected by nonalternant hydrocarbons and their heteroatom derivatives. Here, the synthesis, structure, and magnetic properties of pyrrole-2,5-diyl-linked bis(nitronyl nitroxide) and bis(iminonitroxide) diradicals are described. The diradicals show characteristic electron spin resonance spectra in dilute glassy solutions, from which conclusions about the presence of distinct conformations, their symmetry, and interspin distance were made.

CuI-cubane clusters based on 10-(aryl)phenoxarsines and their luminescence.

In this work, we present the synthesis, structural and photophysical characterization, and theoretical study of tetranuclear copper(i) cubane-type Cu4I4 clusters 6-10 with different 10-(aryl)phenoxarsine ligands - 10-(p-fluorophenyl)phenoxarsine (1), 10-(p-ethoxyphenyl)phenoxarsine (2), 10-(phenyl)phenoxarsine (3), 10-(m-fluorophenyl)phenoxarsine (4), and 10-(o-methoxyphenyl)phenoxarsine (5), respectively. The structures of 1-5 were confirmed by NMR spectroscopy, mass spectrometry, elemental analysis and for complexes 6, 7, and 10 by single-crystal X-ray diffraction analysis. The UV/Vis absorption and emission properties were studied and rationalized by DFT and time-dependent DFT calculations.

Pressure-Controlled Migration of Paramagnetic Centers in a Heterospin Crystal.

A study of the single-crystal-to-single-crystal transformation induced by temperature variation for the chain polymer Cu(II) complex with nitronyl nitroxide showed that an increase in the hydrostatic pressure of up to ∼0.07 GPa completely changes the intracrystalline displacements of molecules relative to one another. This, in turn, significantly affects the interaction energy of the unpaired electrons of the paramagnetic centers and hence the form of the temperature dependence of the magnetic susceptibility .

Simultaneous Introduction of Two Nitroxides in the Reaction: A New Approach to the Synthesis of Heterospin Complexes.

A new approach to the synthesis of multispin compounds has been developed, namely, the simultaneous introduction of two different stable nitroxides (nitronyl nitroxide and imino nitroxide) in a reaction with a metal ion. An important characteristic of the new method is that nitronyl nitroxide and imino nitroxide introduced in the reaction with the metal are the products of different series; i.e.

Ytterbium and Europium Complexes of Redox-Active Ligands: Searching for Redox Isomerism.

The reaction of (dpp-Bian)Eu(dme) (3) (dpp-Bian is dianion of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene; dme is 1,2-dimethoxyethane) with 2,2'-bipyridine (bipy) in toluene proceeds with replacement of the coordinated solvent molecules with neutral bipy ligands and affords europium(II) complex (dpp-Bian)Eu(bipy) (9). In contrast the reaction of related ytterbium complex (dpp-Bian)Yb(dme) (4) with bipy in dme proceeds with the electron transfer from the metal to bipy and results in (dpp-Bian)Yb(bipy)(bipẏ) (10) - ytterbium(III) derivative containing both neutral and radical-anionic bipy ligands. Noteworthy, in both cases dianionic dpp-Bian ligands retain its reduction state.

The clinical and laboratory characteristics of acute spontaneous urticaria and its progression to chronic spontaneous urticaria.

Background: The natural history of the progression from acute spontaneous urticaria (ASU) to chronic spontaneous urticaria (CSU), CSU remains poorly understood.

Objective: To identify clinical and laboratory patient attributes that may be predictive of ASU progression to CSU.

Methods: We prospectively studied consecutive adult patients (age ≥ 18 years) with a diagnosis of urticaria of <6 weeks' duration.

A Copper-Nitroxide Adduct Exhibiting Separate Single Crystal-to-Single Crystal Polymerization-Depolymerization and Spin Crossover Transitions.

A complex cascade of solid-state processes initiated by variation of temperature was found for the heterospin complex [Cu(hfac)2L(Me/Et)] formed in the reaction of copper(II) hexafluoroacetylacetonate [Cu(hfac)2] with stable nitronyl nitroxide 2-(1-methyl-3-ethyl-1H-pyrazol-4-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (L(Me/Et)). The cooling of the compound below 260 K initiated a solid-state chemical reaction, which led to a depolymerization of chains and formation of a pair heterospin complex [Cu(hfac)2L(Me/Et)2][[Cu(hfac)2]3L(Me/Et)2]. Further decrease in temperature below 144 K led to a spin transition accompanied by a drastic decrease in the effective magnetic moment from 2.

Double exchange in a mixed-valent octanuclear iron cluster, [Fe8(μ4-O)4(μ-4-Cl-pz)12Cl4](-).

A combination of SQUID and pulsed high-field magnetometry is used to probe the nature of mixed valency in an Fe(II)Fe7(III) cluster. DFT-computed spin Hamiltonian parameters suggest that antiferromagnetic coupling dominates, and that electron transfer both between the four irons of the cubane core (t1) and between a cubane and three neighboring irons (t2) is significant. Simulations using the computed parameters are able to reproduce the key features of the measured effective magnetic moment, μeff(T), over the 2 < T < 300 K temperature range.

Detailed EPR study of spin crossover dendrimeric iron(III) complex.

The unusual magnetic behavior of the first dendritic Fe(3+) complex with general formula [Fe(L)2](+)Cl(-)·H2O based on a branched Schiff base has been investigated by electron paramagnetic resonance (EPR) and Mössbauer spectroscopy. EPR displays that complex consists of the three types of magnetically active iron centers: one S = 1/2 low-spin (LS) and two S = 5/2 high-spin (HS) centers with strong low-symmetry and weak distorted octahedral crystal fields. Analysis of the magnetic behavior reflected by I versus T (where I is the EPR lines integrated intensity of the spectrum) demonstrates that the dendritic Fe(3+) complex has sufficiently different behavior in three temperature intervals.

Crucial role of paramagnetic ligands for magnetostructural anomalies in "breathing crystals".

Breathing crystals based on polymer-chain complexes of Cu(hfac)(2) with nitroxides exhibit thermally and light-induced magnetostructural anomalies in many aspects similar to a spin crossover. In the present work, we report the synthesis and investigation of a new family of Cu(hfac)(2) complexes with tert-butylpyrazolylnitroxides and their nonradical structural analogues. The complexes with paramagnetic ligands clearly exhibit structural rearrangements in the copper(II) coordination units and accompanying magnetic phenomena characteristic for breathing crystals.

Theoretical analysis of spin crossover in iron(II) [2×2] molecular grids.

We use quantum-chemical density functional theory calculations to elucidate the origin of spin-crossover pathways in two iron(II) [2×2] molecular grids with carbohydrazide-based bridging ligands. The complexes are characterized energetically and structurally in five available spin states. Special attention is paid to analysis of the structural distortion induced on each iron center by spin transition on any of its neighbors.

Spin crossover in tetranuclear cyanide-bridged iron(II) square complexes: a theoretical study.

Spin crossover in a series of six cyanide-bridged iron(II) tetranuclear square complexes was analyzed using density functional theory (DFT) methods. As the spin crossover between the low-spin (LS) and high-spin (HS) states can occur only for two of four iron ions, we characterized energetically and structurally the [LS-LS], [HS-LS], and [HS-HS] spin-state isomers. For all studied complexes, the energy of the mixed [HS-LS] spin state does not deviate essentially from the halfway point between the energies of homogeneous spin states, thereby satisfying the conditions for an one-step transition between the [LS-LS] and [HS-HS].

Experimental and theoretical Mössbauer study of an extended family of [Fe8(μ4-O)4(μ-4-R-px)12X4] clusters.

Six [Fe(8)(μ(4)-O)(4)(μ-4-R-pyrazolato)(12)X(4)] complexes containing an identical Fe(8)(μ(4)-O)(4) core have been structurally characterized and studied by Mössbauer spectroscopy. In each case, an inner μ(4)-O bridged Fe(III) cubane core is surrounded by four trigonal bipyramidal iron centers, the two distinct sites occurring in a 1:1 ratio. The Mössbauer spectrum of each of the clusters consists of two quadrupole doublets, which, with one exception (X = NCS, R = H), overlap to give three absorption lines.

Redox potential of the Rieske iron-sulfur protein quantum-chemical and electrostatic study.

Quantum-chemical study of structures, energies, and effective partial charge distribution for several models of the Rieske protein redox center is performed in terms of the B3LYP density functional method in combination with the broken symmetry approach using three different atomic basis sets. The structure of the redox complex optimized in vacuum differs markedly from that inside the protein. This means that the protein matrix imposes some stress on the active site resulting in distortion of its structure.

Electronic structure and magnetic properties of a trigonal prismatic Cu(II)6 cluster.

A combination of detailed magnetisation studies and electronic-structure analysis using broken-symmetry DFT is used to explore the electronic structure of a trigonal prismatic Cu(II)(6) cluster. The presence of six paramagnetic metal centres with S = 1/2 gives rise to a maximum multiplicity of S = 3 and a total of 31 broken-symmetry states with M(S) < 3. Computed differences in energy between the high-spin and broken-symmetry states are expressed in terms of the 15 distinct Heisenberg exchange coupling parameters, J(ij), and the equations are solved by a least-squares fitting procedure.

Fe2 and Fe4 clusters encapsulated in vacant polyoxotungstates: hydrothermal synthesis, magnetic and electrochemical properties, and DFT calculations.

While the reaction of [PW(11)O(39)](7-) with first row transition-metal ions M(n+) under usual bench conditions only leads to monosubstituted {PW(11)O(39)M(H(2)O)} anions, we have shown that the use of this precursor under hydrothermal conditions allows the isolation of a family of novel polynuclear discrete magnetic polyoxometalates (POMs). The hybrid asymmetric [Fe(II)(bpy)(3)][PW(11)O(39)Fe(2) (III)(OH)(bpy)(2)]12 H(2)O (bpy=bipyridine) complex (1) contains the dinuclear {Fe(micro-O(W))(micro-OH)Fe} core in which one iron atom is coordinated to a monovacant POM, while the other is coordinated to two bipyridine ligands. Magnetic measurements indicate that the Fe(III) centers in complex 1 are weakly antiferromagnetically coupled (J=-11.

A mixed-valence polyoxovanadate(III,IV) cluster with a calixarene cap exhibiting ferromagnetic V(III)-V(IV) interactions.

A series of compounds (cat)[V6O6(OCH3)8(calix)(CH3OH)] was obtained under anaerobic conditions and solvothermal reaction of VOSO4 with p-tert-butylcalix[4]arene (calix) in methanol using different types of bases (Et4NOH, NH4OH, pyridine, Et3N). All compounds contain the same polyoxo(alkoxo)hexavanadate anion [V6O6(OCH3)8(calix)(CH3OH)]- (1) exhibiting a mixed valence {VIIIVIV5O19} core with the so-called Lindqvist structure coordinated to a calix[4]arene macrocycle and cocrystallizing with the conjugated acid of the base (cat = Et4N+, NH4(+), pyridinium, Et3NH+) involved in the synthesis process. The structures have been fully established from X-ray diffraction on single crystals and the mixed valence state has been confirmed by bond valence sum calculations.

Catalytic alcohol oxidation by an unsymmetrical 5-coordinate copper complex: electronic structure and mechanism.

Density functional theory reveals the detailed mechanism of alcohol oxidation by a model copper complex, Cu(II)L, L = cis-1-(3',5'-dimethoxy-benzylideneamino)-3,5-[2-hydroxy-(3',5'-di-tert-butyl)benzylideneimino]cyclohexane. Despite the obvious structural and functional parallels between the title compound and the enzyme galactose oxidase, the details of the catalytic pathway are fundamentally different. In the enzyme, coordination of the substrate produces an active form containing a Cu(II) centre and a tyrosyl radical, the latter being responsible for the abstraction of hydrogen from the substrate.