Solvatochromism of thiocyanato-tetraazamacrocycle-manganese(III) complexes

Summary Solvent effects on thecharge-transfer bands of a series of thiocyanato-tetraazamacrocycle-manganese(III) complexes are reported, and discussed in terms of the donor and acceptor (hydrogen-bonding) properties of the respective solvents. The piezochromic behaviour of one of these complexes is also described.

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Solvatochromie von Thiocyanato-Tetraazamakrocyclo-Mangan(III) — Komplexen

Zusammenfassung Die Auswirkung von Lösungsmitteleffekten auf diecharge-transfer — Banden einer Reihe von Thiocyanato-Tetraazamakrocyclo-Mangan(III) — Komplexen wird im Zusammenhang mit den Donor- und Akzeptoreigenschaften des Lösungsmittels diskutiert. Das piezochrome Verhalten eines der Komplexe wird beschrieben.

     

氧化锰三维微型超级电容器电极制备及电化学特性

为增强电容器的电荷贮存能力,用MEMS技术在玻璃上制备高深宽比三维微电极结构,以增大电极的表面积,用阳极恒电压沉积在微电极表面沉积氧化锰作为电极活性物质,用循环伏安和恒流充放电方法对所备的电极进行了电化学性能测试,并用无结构的二维电极进行对比实验. 结果表明,三维电极结构能有效增强电容器的电荷贮存能力,在1.0 mA/cm²的充放电密度下,三维电极的单位底面积比电容达17.88 mF/cm²,是相应二维电极的7倍.     

Continuous multi-element (Cu, Mn, Ni, Se) monitoring in saline and cell suspension using on-line microdialysis coupled with simultaneous electrothermal atomic absorption spectrometry

We have developed a microdialysis sampling technique coupled on-line with simultaneous electrothermal atomic absorption spectrometry (SIMAAS) for the continuous monitoring of copper (Cu), manganese (Mn), nickel (Ni), and selenium (Se) in saline solutions and in cell suspensions. These trace elements are considered to be those associated most significantly with oxidative stress in biological systems. We employed ultrapure saline (0.9% NaCl) as the perfusate and, thus, the dialysate samples contained a high concentration of salt in the matrix. The use of modifiers [Pd coupled with Mg(NO₃)₂] prevented the target elements from undergoing evaporation at a pyrolysis temperature of 1200 °C, a process that effectively eliminated interference from NaCl. The excellent linearity, detection limits, and precision of the SIMAAS technique allowed the Cu, Mn, Ni, and Se concentrations to be determined in saline. For the on-line microdialysis-SIMAAS system, the ultrapure saline was perfused at a flow rate of 1 μL/min. The probe recoveries of Cu, Mn, Ni, and Se in saline were 57.9, 65.0, 65.5, and 67.9%, respectively. A standard saline solution was measured continuously by the on-line system to ensure long-term stability; each measurement fell within a range of two standard deviations. We determined the on-line spiked recoveries of Cu, Mn, Ni, and Se (101.3, 88.8, 91.3, and 98.5%, respectively) by adding a spiking standard into the stirred saline. The spiked recoveries (Cu, 37.5%; Mn, 3.8%; Ni, 71.1%; Se, 33.8%) were also determined through on-line spiking of a standard into the stirred cell suspension; these values demonstrate that Cu, Mn, and Se were depleted in the cell suspension, but Ni was not. The use of this on-line microdialysis-SIMAAS system permitted the in situ, dynamic, and continuous monitoring of Cu, Mn, Ni, and Se in cell suspensions at a temporal resolution of 20 min.     

Template-free synthesis of MnO2 nanowires with secondary flower like structure: Characterization and supercapacitor behavior studies

Manganese dioxide (MnO₂) nanowires with diameter about 30-70 nm is achieved via a two-step process: first, template-free cathodic electrodeposition from aqueous solution of Mn(NO₃)₂ on steel substrate and followed by heat treatment. The temperature-annealed sample was studied by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) methods and Fourier transform infrared (FT-IR) spectroscopy. The electrochemical performance of the MnO₂ sample was studied by cyclic voltammetry (CV) and chronopotentiometry in Na₂SO₄ solutions. The sample showed excellent supercapacitive behavior. The specific capacitance (SC) of 237 F g⁻¹ in a potential window of 0-0.9V was obtained at the scan rate of 2 mV s⁻¹. The SC calculated from the chronopotentiometry data is about 246 F g⁻¹. The SC was decreased by 16% after 1000 cycles.     

Investigations of 2-Thiazoline-2-thiol as a Ligand: Synthesis and X-ray Structures of [Mn2(CO)7(μ-NS2C3H4)2] and [Mn(CO)3(PPh3)(κ2-NS2C3H4)]

Abstract  Treatment of Mn₂(CO)₁₀ with 2-thiazoline-2-thiol in the presence of Me₃NO at room temperature afforded the dimanganese complexes [Mn₂(CO)₇(μ-NS₂C₃H₄)₂] (1) and [Mn₂(CO)₆(μ-NS₂C₃H₄)₂] (2) in 51 and 34% yields, respectively. Compound 1 was quantitatively converted into 2 when reacted with one equiv of Me₃NO. Reaction of 1 with triphenylphosphine at room temperature furnished the mononuclear complex [Mn(CO)₃(PPh₃)(κ ²-NS₂C₃H₄)] (3) in 66% yield. All three new complexes have been characterized by elemental analyzes and spectroscopic data together with single crystal X-ray diffraction studies for 1 and 3. Compound 1 crystallizes in the orthorhombic space group Pbca with a = 12.4147(2), b = 16.2416(3), c = 19.0841(4) ?, β = 90°, Z = 8 and V = 3848.01(12) ?³ and 3 crystallizes in the monoclinic space group P 2₁/n with a = 10.41730(10), b = 14.7710(2), c = 14.9209(2) ?, β = 91.1760(10)°, Z = 4 and V = 2295.45(5) ?³. Graphical Abstract  Two new dimanganese complexes [Mn₂(CO)₇(μ-NS₂C₃H₄)₂] (1) and [Mn₂(CO)₆(μ-NS₂C₃H₄)₂] (2) were formed when [Mn₂(CO)₁₀] was treated with 2-thiazoline-2-thiol in the presence of Me₃NO. Compound 2 reacts with PPh₃ to give the monomeric complex [Mn(CO)₃(PPh₃ )(κ ²-NS₂C₃H₄)]. The structures of 1 and 3 were established by crystallography. Shishir Ghosh, Faruque Ahmed, Rafique Al-Mamun, Daniel T. Haworth, Sergey V. Lindeman, Tasneem A. Siddiquee, Dennis W. Bennett, Shariff E. Kabir Investigations of 2-thiazoline-2-thiol as a ligand: Synthesis and X-ray structures of [Mn₂(CO)₇(μ-NS₂C₃H₄)₂] and [Mn(CO)₃ (PPh3)(κ ²-NS₂C₃H₄)].      

A variety of new tri- and tetranuclear Mn–Ln and Fe–Ln (Ln = lanthanide) complexes

The use of carboxylates in the synthesis of 3d/4f clusters, with or without a second organic ligand, has afforded a series of tetranuclear M₂Gd₂ complexes (M = Fe or Mn), and two new trinuclear M₂Gd (M = Fe or Mn) molecular compounds. Only one of these, [Mn₂Gd₂O₂(O₂CBu^t)₈(HO₂CBu^t)₄] (1), does not contain a multidentate chelate ligand. Two other similar tetranuclear clusters were synthesized from the use of triethanolamine (teaH₃) and 1,1,1-tris(hydroxymethyl)ethane (thmeH₃). [Mn₂Gd₂(OH)₂(O₂CPh)₄(NO₃)₂(teaH)₂] (2) has very similar structure with 1, bearing a defective incomplete double-cubane core bridged by μ₃-O atoms, whereas in the core of [NHEt₃]₂[Fe₂Gd₂(O₂CPh)₄(thme)₂(NO₃)₄] (3) the thme³⁻ ligand caps the two incomplete cubane units, providing the triply-bridging alkoxides needed for bridging. Two new oxide-centered triangular clusters were synthesized bearing the Schiff-based chelate 2-{[2-(dimethylamino)ethyl]methylamino}ethanol (dmemH), namely [Fe₂GdO(O₂CBu^t)₂(dmem)₂(NO₃)₃] (4), and [Mn₂GdO(O₂CBu^t)₂(dmem)₂(NO₃)₃] (5). Magnetic susceptibility measurements and/or reduced magnetization studies established that complexes 1 and 3 have an S = 5 ground state, complex 2 has S = 4, and complexes 4 and 5 are S = 7/2 in their ground states. These complexes portray the feasibility of obtaining products bearing metal cores commonly found in homometallic clusters, even when these include metals with completely different coordination chemistry and electronic structure, such as lanthanides.     

Equilibrium and kinetic studies of reactions of [MnN(H2O)(CN)4] with monodentate ligands and the molecular structure of [MnN(NCS)(CN)4]

The dissolution of [(CH₃)N]₂Na[MnN(CN)₅]·H₂O in water results in the dissociation of the labile trans-CN ligand to form [MnN(H₂O)(CN)₄]²⁻(aq). The formed aqua complex reacts rapidly with a number of nucleophiles such as NCS⁻ and N₃⁻. Here we report the single crystal X-ray structure of the reaction products of as well as the equilibrium and kinetic behaviour of [MnN(H₂O)(CN)₄]²⁻ in solution.     

Solid–liquid phase equilibria in the system K2SO4–MnSO4–H2O at 298 K and 313 K

Phase equilibria studies of the system K₂SO₄–MnSO₄–H₂O published revealed discrepancies between the data presented in the literature regarding the solid phases formed at ambient temperatures. The solubility in the system at 298 K and 313 K was determined. At 298 K, the existence of the double salt K₂SO₄·3MnSO₄·5H₂O and of MnSO₄·H₂O was confirmed. The examinations at 313 K showed the formation of the stable solid phases MnSO₄·H₂O, K₂SO₄·2MnSO₄, K₂SO₄·MnSO₄·1.5H₂O, K₂SO₄ and the formation of a metastable phase K₂SO₄·MnSO₄·2H₂O.     

Synthesis, crystal structures and magnetic properties of trinuclear oxo-centered homo- and mixed-valence manganese pivalate complexes with imidazole (Im) and 1-methylimidazole (1-MeIm): and

Two new μ₃-oxo-centered trinuclear manganese complexes, one of them a homo-valence (1) pivalate complex and the other a mixed-valence (2) pivalate complex (where Im = imidazole, 1-MeIm = 1-methylimidazole), have been synthesized and characterized by IR spectroscopy, thermogravimetric analysis, X-ray crystallography and magnetochemistry. Complexes 1 and 2 are μ₃-oxo-trinuclear compounds with the three manganese atoms bridged by six pivalate groups. At each axial position there is an Im (1) or 1-MeIm (2) molecule. In both compounds, the manganese coordination geometry is slightly distorted octahedral, consisting of the oxygen of the central triangle, four oxygen atoms from bridging pivalate ligands, and a terminal Im or 1-MeIm nitrogen atom. The crystal packing of 1 involves hydrogen bonding between complex cations [Mn₃O(Piv)₆(Im)₃]⁺ and outersphere pivalate ions, whereas in compound 2 interactions of the C–Hπ type, formed by both the aromatic and methyl C–H groups of 1-MeIm molecules, are present. Magnetic studies reveal that both compounds represent antiferromagnetically coupled, spin-frustrated triangular systems exhibiting weak to moderate exchange coupling constants.     

苯甲酸气相加氢合成无氯苯甲醛用MnOx/Al2O3催化剂

采用共沉淀法制备了一系列ＭｎＯｘ／γ－Ａｌ２Ｏ３催化剂，并利用连续流动反应装置考察了它们对苯甲酸加氢制苯甲醛反应的催化性能，结果表明，催化剂结本反应有理想的反应活性和选择性，催化剂Ｍｎ载量为１０％～２０％及反应温度为６９３Ｋ时，苯甲酸转化率为９９％，苯甲醛选择性为９６％，ＢＥＴ比表面积测定结果反映了焙烧温度和活性组分载量对催化剂比表面积的影响，ＸＲＤ结果揭示了催化剂还原前后的物分别为Ｍｎ２Ｏ３和Ｍ