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The crystal structure of cis-[Cu(C8H7O3)(2)(H2O)(2)] (115 K data) reveals bidentate vanillinate ions coordinated via methoxy and deprotonated hydroxy oxygen atoms and water molecules in a distorted octahedral CuO6 chromophore. A cis orientation of the ligands enables two non-identical O(methoxy)-Cu-O(water) coordination axes (2.354(l) + 2.163(1); 2.151(1) + 2.020(1) angstrom), and the third shortest O(hydroxy)-Cu-O(hydroxy) axis (1.919(1) + 1.914(1) angstrom). This 115 K coordination sphere differs importantly to the one obtained from the 293 K data of the same compound, where two long 0(methoxy)-Cu-O(water) axes are of the same length, and only minor changes at the short 0(hydroxy)-Cu-O(hydroxy) axis are noticed. An axial symmetry of the complex with an inverse g(1.2)(g(perpendicular to)) > g(3)(g(parallel to)) pattern is observed in the temperature range from 298 to 180 K. A further decrease of temperature reveals gradual changes from axial to rhombic symmetry (g(1) > g(2) > g(3)) that is reversible. A mean-square displacement amplitude (MDSA) analysis reveals a disorder in the Cu-O(methoxy) bonds, but not in the other metal-ligand Cu-O(hydroxy) and Cu-O(water) bonds at 293 and 115 K. The disorder is significantly weaker in the 115 K structure. The MSDA analysis and the structural-EPR agreement show vibrational disorder in two coordination axes, due to the cis conformation of the complex with two 0(methoxy)-Cu-O(water) axes.
Deprotonation of ligand-appended alkoxyl groups in mononuclear copper(II) complexes of N,O ligands L-1 and L-2, gave dinuclear complexes sharing symmetrical Cu2O2 cores. Molecular structures of these mono-and binuclear complexes have been characterized by XRD, and their electronic structures by UV/Vis, H-1 NMR, EPR and DFT; moreover, catalytic performance as models of catechol oxidase was studied. The binuclear complexes with anti-ferromagnetically coupled copper(II) centers are moderately active in quinone formation from 3,5-di-tert-butyl-catechol under the estab-lished conditions of oxygen saturation, but are strongly activated when additional dioxygen is administered during catalytic turnover. This unforeseen and unprecedented effect is attributed to increased maximum reaction rates v(max), whereas the substrate affinity KM remains unaffected. Oxygen administration is capable of (partially) removing limitations to turnover caused by product inhibition. Because product inhibition is generally accepted to be a major limitation of catechol oxidase models, we think that our observations will be applicable more widely.
Magnetosome Organization in Magnetotactic Bacteria Unraveled by Ferromagnetic Resonance Spectroscopy
(2017)
Magnetotactic bacteria form assemblies of magnetic nanoparticles called magnetosomes. These magnetosomes are typically arranged in chains, but other forms of assemblies such as clusters can be observed in some species and genetic mutants. As such, the bacteria have developed as a model for the understanding of how organization of particles can influence the magnetic properties. Here, we use ferromagnetic resonance spectroscopy to measure the magnetic anisotropies in different strains of Magnetosprillum gtyphiswaldense MSR-1, a bacterial species that is amendable to genetic mutations. We combine our experimental results with a model describing the spectra. The model includes chain imperfections and misalignments following a Fisher distribution function, in addition to the intrinsic magnetic properties of the magnetosomes. Therefore, by applying the model to analyze the ferromagnetic resonance data, the distribution of orientations in the bulk sample can be retrieved in addition to the average magnetosome arrangement. In this way, we quantitatively characterize the magnetosome arrangement in both wild-type cells and Delta mamJ mutants, which exhibit differing magnetosome organization.
Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry.
Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry.
EPR spectroscopy is a well suited analytical tool to monitor the electronic situation around paramagnetic metal centres as copper(II) and therefore the structural influences on the paramagnetic ion. 1,2-Dithiosquaratometalates are available by direct synthesis from metal salts with dipotassium-1,2-dithiosquarate and the appropriate counter cations. Synthesis and characterisation of bis(benzyltributylammonium)1,2-dithiosquaratonickelate(II), (BzlBu(3)N)(2)[Ni(dtsq)(2)], and bis(benzyltributylammonium)1,2-dithiosquaratocuprate(II), (BzlBu(3)N)(2)[Cu(dtsq)(2)], with benzyltributylammonium as the counter ion is reported and the X-ray structures of two complexes, (BzlBu(3)N)(2)[Ni(dtsq)(2)] and (BzlBu(3)N)(2)[Cu(dtsq)(2)], are presented. Both complexes, crystallising in the monoclinic space group P2(1)/c, are isostructural with only small differences in the coordination sphere due to the different metal ions. The diamagnetic nickel complex is therefore well suited as a host lattice for the paramagnetic Cu(II) complex to measure EPR for additional structural information. (c) 2015 Institute of Chemistry, Slovak Academy of Sciences
Metal-containing ionic liquids (ILs) are of interest for a variety of technical applications, e.g., particle synthesis and materials with magnetic or thermochromic properties. In this paper we report the synthesis of, and two structures for, some new tetrabromidocuprates(II) with several "onium" cations in comparison to the results of electron paramagnetic resonance (EPR) spectroscopic analyses. The sterically demanding cations were used to separate the paramagnetic Cu(II) ions for EPR measurements. The EPR hyperfine structure in the spectra of these new compounds is not resolved, due to the line broadening resulting from magnetic exchange between the still-incomplete separated paramagnetic Cu(II) centres. For the majority of compounds, the principal g values (g|| and g(perpendicular to)) of the tensors could be determined and information on the structural changes in the [CuBr4](2-) anions can be obtained. The complexes have high potential, e.g., as ionic liquids, as precursors for the synthesis of copper bromide particles, as catalytically active or paramagnetic ionic liquids.
Planar bis(1,2-dithiooxalato)nickelate(II), [Ni(dto)]2− reacts in aqueous solutions with lanthanide ions (Ln3+) to form pentanuclear, hetero-bimetallic complexes of the general composition [{Ln(H2O)n}2{Ni(dto)2}3]·xH2O. (n = 4 or 5; x = 9–12). The complex [{Ho(H2O)5}2{Ni(dto)2}3]·10H2O, Ho2Ni3, was synthesized and characterized by single crystal X-ray structure analysis and powder diffraction. The Ho2Ni3 complex crystallizes as monoclinic crystals in the space group P21/c. The channels and cavities, appearing in the crystal packing of the complex molecules, are occupied by a varying amount of non-coordinated water molecules.
1,2-Dithiosquaratonickelates are available by direct synthesis from metal salts with dipotassium-1,2-dithiosquarate and the appropriate counter cations. The synthesis and characterization, including mass spectrometry, of a series 1,2-dithiosquaratonickelates(II), [Ni(dtsq)(2)](2-), with several "onium" cations is reported and the X-ray structures of two diamagnetic complexes, (HexPh(3)P)(2)[Ni(dtsq)(2)] and (BuPh3P)(2)[Ni(dtsq)(2)] with sterically demanding counter ions are presented. The diamagnetic nickel complexes have been doped as host lattices with traces of Cu(II) to measure EPR for additional structural information. The thermal behavior of this series is studied by thermogravimetry and differential thermal analysis (TG/DTA). The thermolysis in air as well as under nitrogen atmosphere of these complexes results in nickel oxide nano-particles in all cases, which are characterized by X-ray powder diffraction.
Protein metal coordination interactions were recently found to function as crucial mechanical cross-links in certain biological materials. Mussels, for example, use Fe ions from the local environment coordinated to DOPA-rich proteins to stiffen the protective cuticle of their anchoring byssal attachment threads. Bioavailability of metal ions in ocean habitats varies significantly owing to natural and anthropogenic inputs on both short and geological spatio-temporal scales leading to large variations in byssal thread metal composition; however, it is not clear how or if this affects thread performance. Here, we demonstrate that in natural environments mussels can opportunistically replace Fe ions in the DOPA coordination complex with V and Al. In vitro removal of the native DOPA metal complexes with ethylenediaminetetraacetic acid and replacement with either Fe or V does not lead to statistically significant changes in cuticle performance, indicating that each metal ion is equally sufficient as a DOPA cross-linking agent, able to account for nearly 85% of the stiffness and hardness of the material. Notably, replacement with Al ions also leads to full recovery of stiffness, but only 82% recovery of hardness. These findings have important implications for the adaptability of this biological material in a dynamically changing and unpredictable habitat.