Iridium Complexes with BIAN-Type Ligands: Synthesis, Structure and Redox Chemistry.

A series of iridium complexes with bis(diisopropylphenyl)iminoacenaphtene (dpp-bian) ligands, [Ir(cod)(dpp-bian)Cl] (), [Ir(cod)(NO)(dpp-bian)](BF) () and [Ir(cod)(dpp-bian)](BF) (), were prepared and characterized by spectroscopic techniques, elemental analysis, X-ray diffraction analysis and cyclic voltammetry (CV). The structures of - feature a square planar backbone consisting of two C = C π-bonds of 1,5-cyclooctadiene (cod) and two nitrogen atoms of dpp-bian supplemented with a chloride ion (for ) or a NO group (for ) to complete a square-pyramidal geometry. In the nitrosyl complex , the Ir-N-O group has a bent geometry (the angle is 125°).

Novel Copper(II) Complexes with Dipinodiazafluorene Ligands: Synthesis, Structure, Magnetic and Catalytic Properties.

The reactions of CuX (X = Cl, Br) with dipinodiazafluorenes yielded four new complexes [CuXL] (X = Cl (), Br (), L = (1R,3R,8R,10R)-2,2,9,9-Tetramethyl-3,4,7,8,9,10-hexahydro-1H-1,3:8,10-dimethanocyclopenta [1,2-b:5,4-b']diquinolin-12(2H)-one) and [(CuX)L]n (X = Cl (), Br (), L = (1R,3R,8R,10R,1'R,3'R,8'R,10'R)-2,2,2',2',9,9,9',9'-Octamethyl-1,1',2,2',3,3',4,4',7,7',8,8',9,9',10,10'-hexadecahydro-1,3:1',3':8,10:8',10'-tetramethano-12,12'-bi(cyclopenta [1,2-b:5,4-b']diquinolinylidene). The complexes were characterized by IR and EPR spectroscopy, HR-ESI-MS and elemental analysis. The crystal structures of compounds , and were determined by X-ray diffraction (XRD) analysis.

Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties.

A new monoiminoacenaphthenone 3,5-(CF)CH-mian (complex ) was synthesized and further exploited, along with the already known monoiminoacenaphthenone dpp-mian, to obtain oxidovanadium(IV) complexes [VOCl(dpp-mian)(CHCN)] () and [VOCl(3,5-(CF)CH-bian)(HO)][VOCl(3,5-(CF)CH-bian)]·2.85DME () from [VOCl(CHCN)(HO)] () or [VCl(THF)]. The structure of all compounds was determined using X-ray structural analysis.

Nitric oxide release and related light-induced cytotoxicity of ruthenium nitrosyls with coordinated nicotinate derivatives.

The synthetic approaches for the preparation of (NO,OH)-(NO,NO)-[RuNO(L)(NO)OH], where L = ethyl nicotinate (I) and methyl nicotinate (II), are reported. The structures of the complexes are characterized by X-ray diffraction and analyzed by Hirshfeld surface analysis. Both compounds show a nitric oxide release reaction under 445 or 532 nm irradiation of dimethyl sulfoxide (DMSO) solutions, which is studied by combined ultraviolet-visible- (UV-vis), infrared- (IR), and electron paramagnetic resonance (EPR) spectroscopy and density functional theory (DFT) calculations.

Synthesis, Structure, and Spectroscopic Study of Redox-Active Heterometallic Cluster-Based Complexes [ReMoSe(CN)].

The heterometallic cluster-based compound K[ReMoSe(CN)] was obtained by high-temperature reaction from a mixture of ReSe and MoSe in molten potassium cyanide. The redox behavior of the [ReMoSe(CN)] cluster anion was studied by cyclic voltammetry in aqueous and organic media showing two reversible one-electron-redox transitions with of -0.462 and 0.

Paramagnetic Rhenium Iodide Cluster with N-Heterocyclic Carbene.

-Trirhenium nonaiodide ReI reacts with 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes) to produce the novel 13-electron paramagnetic cluster ReI(IMes), which was characterized by means of X-ray diffraction analysis, ESR spectroscopy, magnetometry, and quantum chemistry.

A Sterically Hindered Derivative of 2,1,3-Benzotelluradiazole: A Way to the First Structurally Characterised Monomeric Tellurium-Nitrogen Radical Anion.

Interaction of the tetradentate redox-active 6,6'-[1,2-phenylenebis(azanediyl)]bis(2,4-di-tert-butylphenol) (H L) with TeCl leads to neutral diamagnetic compound TeL (1) in high yield. The molecule of 1 has a nearly planar TeN O fragment, which suggests the formulation of 1 as Te L , in agreement with the results of DFT calculations and QTAIM and NBO analyses. Reduction of 1 with one equivalent of [CoCp ] leads to quantitative formation of the paramagnetic salt [CoCp ] [1] , which was characterised by single-crystal XRD.

Temperature- and excitation wavelength-dependent emission in a manganese(ii) complex.

A mononuclear manganese(ii) complex with a chelating 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine ligand (L), [MnLCl]·HO, shows intriguing excitation wavelength-dependent emission. Depending on the excitation wavelength, the complex demonstrates three emission bands with the maxima at 380 nm, 440 nm and 495 nm. The 380 nm and 440 nm emissions originate from the π → π* and n → π* ligand-centered transitions.

23-Electron Octahedral Molybdenum Cluster Complex [{MoI}Cl].

Photoactive transition metal compounds that are prone to reversible redox reactions are important for myriad applications, including catalysis, optoelectronics, and sensing. This article describes chemical and electrochemical methods to prepare cluster complex (BuN)[{MoI}Cl], a rare example of a 23 e cluster complex within the family of octahedral clusters of Mo, W, and Re. The low temperature and room temperature crystal structures; electronic structure; and the magnetic, optical, and electrochemical properties of this complex are described.

Bismuth germanate as a perspective material for dielectric resonators in EPR spectroscopy.

High purity bismuth germanate (Bi4(GeO4)3, BGO) is proposed and implemented as an alternative material for dielectric EPR resonators. A significant improvement of the absolute sensitivity can be readily achieved by substituting the alumina insert (ring) by BGO-made one in commercially available X-band EPR probeheads. Four BGO dielectric inserts of 2, 3, 4 and 5mm inner diameter (ID) were made for comparison with standard 5mm inner diameter alumina insert.

Volatile Heterobimetallic Complexes from Pd and Cu β-Diketonates: Structure, Magnetic Anisotropy, and Thermal Properties Related to the Chemical Vapor Deposition of CuPd Thin Films.

A novel approach for preparing volatile heterometallic complexes for use as precursors for the chemical vapor deposition of various materials is reported. New CuPd complexes based on β-diketonate units were prepared, and their structures and compositions were determined. [PdL *CuL ] (1) and [PdL *Cu(tmhd) ] (2) (L=2-methoxy-2,6,6-trimethylheptane-3,5-dionate; tmhd=2,2,6,6- tetramethylheptane-3,5-dionate) are 1D coordination polymers with alternating metal complexes, which are connected through weak interactions between the Cu atoms and the OCH groups from the ligand of the Pd complexes.

Formation of ordered films of axially bridged aluminum phthalocyanine [(tBu)4PcAl]2O via magnetic field-induced reaction.

The μ-(oxo)bis[tetra-tert-butylphthalocyaninato] aluminum(III) [(tBu)4PcAl]2O films with the crystallites oriented preferably in one direction were obtained via chemical transformation of tetra-tert-butylsubstituted chloroaluminum(III) phthalocyanine (tBu)4PcAlCl film upon its annealing in magnetic field. A comparative analysis of the influence of post-deposition annealing process without and under applied magnetic field of 1 T, on the orientation and morphology of (tBu)4PcAlCl and [(tBu)4PcAl]2O films, has been carried out by the methods of UV-vis, Infrared and Raman spectroscopies, XRD as well as atomic force microscopy. The formation of [(tBu)4PcAl]2O films with elongated crystallites having preferential orientation was observed upon heating of the films in magnetic field while annealing without magnetic field under the same conditions does not demonstrate any effect on the structure and morphology of these films.

Heterometallic clusters with a new {Re3Mo3S8} core: direct synthesis, properties and DFT calculations.

We report the direct facile high-temperature synthesis and investigation of heterometallic rhenium-molybdenum cluster K6[Re3Mo3S8(CN)4(CN)2/2] (1) with a new {Re3Mo3S8} core. Dissolution of polymeric compound 1 resulted in subsequent oxidation and formation of stable 23e paramagnetic anionic cluster complex [Re3Mo3S8(CN)6](6-).