@article{GhaisariWinklhoferStrauchetal.2017, author = {Ghaisari, Sara and Winklhofer, Michael and Strauch, Peter and Klumpp, Stefan and Faivre, Damien}, title = {Magnetosome Organization in Magnetotactic Bacteria Unraveled by Ferromagnetic Resonance Spectroscopy}, series = {Biophysical journal}, volume = {113}, journal = {Biophysical journal}, publisher = {Cell Press}, address = {Cambridge}, issn = {0006-3495}, doi = {10.1016/j.bpj.2017.06.031}, pages = {637 -- 644}, year = {2017}, abstract = {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.}, language = {en} } @article{ZabelWinterKellingetal.2016, author = {Zabel, Andr{\´e} and Winter, Alette and Kelling, Alexandra and Schilde, Uwe and Strauch, Peter}, title = {Tetrabromidocuprates(II)-Synthesis, Structure and EPR}, series = {International journal of molecular sciences}, volume = {17}, journal = {International journal of molecular sciences}, number = {4}, publisher = {MDPI}, address = {Basel}, doi = {10.3390/ijms17040596}, pages = {14}, year = {2016}, abstract = {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 gK) 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.}, language = {en} } @misc{ZabelWinterKellingetal.2016, author = {Zabel, Andr{\´e} and Winter, Alette and Kelling, Alexandra and Schilde, Uwe and Strauch, Peter}, title = {Tetrabromidocuprates(II)-Synthesis, Structure and EPR}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-91470}, pages = {14}, year = {2016}, abstract = {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 gK) 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.}, language = {en} } @article{SieboldKellingSchildeetal.2005, author = {Siebold, M. and Kelling, Alexandra and Schilde, Uwe and Strauch, Peter}, title = {Heterobimetallic 3d-4-complexes with bis(1;2-dithiooxalato)nickelate(II) as planar bridging block}, issn = {0932-0776}, year = {2005}, abstract = {Planar bis(1,2-dithiooxalato)nickelates(II) react in aqueous solutions of lanthanide ions to form pentanuclear, heterobimetallic complexes of the general composition [{Ln(H2O)(n)}(2)- {Ni(dto)(2)}(3)] (.) xH(2)O (Ln = Y3+, La3+, Ce3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+; n = 4 or 5; x = 9-12). With [{Nd(H2O)(5)}(2){Ni(S2C2O2)(2)}(3)] (.) xH(2)O (x = 10-12) (1) and [{Er(H2O)(4)}(2){Ni(S2C2O2)(2)}(3)] (.) xH(2)O (x = 9- 10) (2) we were able to isolate two complexes of this series as single crystals, which were characterized by X-ray structure analysis. Depending on the individual ionic radii of the lanthanide ions, the compounds crystallize in two different crystal systems with the following unit cell parameters: 1, monoclinic in P2(1)/c with a = 11.3987(13), b = 11.4878(8), c = 20.823(2)angstrom , beta = 98.907(9)degrees and Z = 2; 2, triclinic in P (1) over bar with a = 10.5091(6), b = 11.0604(6), c = 11.2823(6) angstrom, alpha = 107.899(4)degrees, beta = 91.436(4)degrees, gamma = 112.918(4)degrees and Z = 1. The channels and cavities appearing in the packing of the molecules are occupied by uncoordinated water molecules. High magnetic moments up to 14.65 BM./f.u. have been observed at room temperature due to the combined moments of the individual lanthanide ions}, language = {en} } @article{KozlevcarHumarStrauchetal.2005, author = {Kozlevcar, Bojan and Humar, M. B. and Strauch, Peter and Leban, I}, title = {Fixation of copper(II) ions in aqueous solution to lignin model compound vanillin in an absence of the nitrogen donor ligands : structural and EPR correlation}, year = {2005}, abstract = {In order to elucidate the interactions of copper with wood, three mononuclear copper(II) coordination compounds with a vanillinate anion, cis-[Cu(C8H7O3)(2)(H2O)(2)] (1), trans-[Cu(C8H7O3)(2)(H2O)(2)].2H(2)O (2), and trans- [Cu(C8H7O3)(2)(H2O)(2)] (3), have been characterized. X-ray structure analysis of the cis isomer 1 reveals two bidentate vanillinate ions coordinated via methoxy (Cu-O1 2.260(2) angstrom) and deprotonated hydroxy oxygen atoms (Cu-O2 1.909(2) angstrom), and two water molecules (Cu-O1w 2.087(2) angstrom) in the octahedral CuO6 chromophore. Two axes O1-Cu- O1w' in the octahedron have the same length, while the third axis O2-Cu-O2' is shorter. This is in agreement with the room temperature EPR spectrum of 1, showing two signals (g(12) 2.302, g(3) 2.005), but interestingly, three signals (g(1) 2.393, g(2) 2.214, g(3) 2.010) in the 115 K spectrum were found. The same coordination atoms were found also in the trans isomer 2 (Cu-O2 1.950(2), Cu-O1w 1.994(2), Cu-O1 2.334(2) angstrom), however here, two axes of almost equal length are short (O2-Cu-O2' O1w-Cu-O1w'), while the third axis is longer (O1-Cu-O1'). On the other hand, three (rhombic) signals (g(1) 2.289, g(2) 2.163, g(3) 2.086) in the room temperature EPR spectrum of 2 suggest three different axes in the coordination octahedron. In the EPR spectrum, of the second trans complex 3, a slightly rhombically distorted elongated axial spectrum is found. The 115 K EPR spectra of the two trans complexes 2 and 3 do not differ significantly from the features observed at room temperature. These results indicate that there is not always a straightforward correlation between the results of XRD structure analysis and EPR spectroscopy. Nevertheless, both methods can act also complementarily and give a deeper insight into the nature of copper(II) chromophores}, language = {en} } @article{WenzelWehseSchildeetal.2004, author = {Wenzel, Barbara and Wehse, Burkhard and Schilde, Uwe and Strauch, Peter}, title = {1,2-Dithioquadratato- und 1,2-Dithiooxalatoindate(III) = 1,2-dithiosquarato- and 1,2-dithiooxalatoindates(III)}, year = {2004}, abstract = {Indium(III) chloride forms in water with potassium 1,2-dithiooxalate (dto) and potassium 1,2-dithiosquarate (dtsq) stable coordination compounds. Due to the higher bridging ability of the 1,2-dithiooxalate ligand in all cases only thiooxalate bridged binuclear complexes were found. From 1,2-dithioquadratate with an identical donor atom set mononuclear trischelates could be isolated. Five crystalline complexes, (BzlMe(3)N)(4)[(dto)(2)In(dto)In(dto)(2)] (1), (BzlPh(3)P)(4)[(dto)(2)In(dto)In(dto)(2)] (2), (BzlMe(3)N)(3)[In(dtsq)(3)] (3), (Bu4N)(3)[In(dtsq)(3)] (4) and (Ph4P)[In(dtsq)(2)(DMF)(2)] (5), have been isolated and characterized by X-ray analyses. Due to the type of the complex and the cations involved these compounds crystallize in different space groups with the following parameters: 1, monoclinic in P2(1)/c with a = 14.4035(5) Angstrom, b = 10.8141(5) Angstrom, c = 23.3698(9) Angstrom, beta = 124.664(2)degrees, and Z = 2; 2, triclinic in P (1) over bar with a = 11.3872(7) Angstrom, b = 13.6669(9) Angstrom, c = 17.4296(10) Angstrom, alpha = 88.883(5)degrees, beta = 96.763(1)degrees, gamma = 74.587(5)degrees, and Z = 1; 3, hexagonal in R3 with a = 20.6501(16) Angstrom, b = 20.6501(16) Angstrom, c = 19.0706(13) Angstrom and Z = 6; 4, monoclinic in P21/c with a = 22.7650(15) Angstrom, b = 20.4656(10) Angstrom, c = 14.4770(9) Angstrom, P}, language = {de} } @article{StrehmelRexhausenStrauch2010, author = {Strehmel, Veronika and Rexhausen, Hans and Strauch, Peter}, title = {2,2,6,6-Tetramethylpiperidine-1-yloxyl bound to the imidazolium ion by an acetamido group for investigation of ionic liquids}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2009.11.124}, year = {2010}, abstract = {New spin probes bearing the 2,2,6,6-tetramethylpiperidine-1-yloxyl covalently bound to the imidazolium ion via a methylene spacer and an amide group are synthesized. If the anion is bis(trifluoromethylsulfonylimide) instead of iodide, the new spin probe has a similar structure as that of an ionic liquid. Nevertheless, the new spin probes are useful tools to investigate ionic liquids.}, language = {en} } @article{StrehmelRexhausenStrauch2010, author = {Strehmel, Veronika and Rexhausen, Hans and Strauch, Peter}, title = {Influence of imidazolium bis(trifluoromethylsulfonylimide)s on the rotation of spin probes comprising ionic and hydrogen bonding groups}, issn = {1463-9076}, doi = {10.1039/B920586a}, year = {2010}, abstract = {The influence of the alkyl chain length in 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonylimide)s is studied to explore the rotation of piperidine-1-yloxyl derivatives substituted with either hydrogen bonding hydroxy group or ionic substituents, such as the cationic trimethylammonium or the anionic sulfate group placed at the 4 position. Structural variation of the ionic liquids results in differences of their viscosity influencing the rotation of the spin probes. The size of the average rotational correlation times of the spin probes dissolved in the ionic liquids depends further on the additional substituent in 4-position at these spin probes. The rotational correlation time exhibits a linear dependence on the ionic liquid viscosity in the case of the spin probe forming hydrogen bonding with the ionic liquids. In contrast to this, a deviation from the Stokes-Einstein behavior is found in the case of rotation of the charged spin probes in the 1-alkyl-3-methylimidazolium bis( trifluoromethylsulfonylimide) s substituted with a longer alkyl chain. This effect may be explained by phase separation on a molecular level between the charged part of the ionic liquid and the longer alkyl chains bound at the imidazolium ion. Although the neutral and the cationic spin probes show only a slight dependence between ionic liquid structure variation and the hyperfine coupling constants, structural effects cause changes in the hyperfine coupling constants in the case of the anionic spin probes. These probes strongly interact with the imidazolium ion.}, language = {en} } @article{StrehmelRexhausenStrauchetal.2010, author = {Strehmel, Veronika and Rexhausen, Hans and Strauch, Peter and Strehmer, Bernd}, title = {Temperature dependence of interactions between stable piperidine-1-yloxyl derivatives and a semicrystalline ionic liquid}, issn = {1439-4235}, doi = {10.1002/cphc.200900977}, year = {2010}, abstract = {The stable 2,2,6,6-tetramethylpiperidine-1-yloxyl and its derivatives with hydrogen-bond-forming (-OH, -OSO3H), anionic (-OSO3- bearing K+ or [K(18-crown-6)](+) as counter ion), or cationic (-N+-(CH3)(3) bearing I-, BF4-, PF6- or N- (SO2CF3)(2) as counter ion) substituents are investigated in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide over a wide temperature range. The temperature dependence of the viscosity of the ionic liquid is well described by the Vogel-Fulcher-Tammann equation. Interestingly, the temperature dependence of the rotational correlation time of the spin probes substituted with either a hydrogen-bond-forming group or an ionic substituent can be described using the Stokes-Einstein equation. In contrast, the temperature dependence of the rotational correlation time of the spin probe without an additional substituent at the 4-position to the nitroxyl group does not follow this trend. The activation energy for the mobility of the unsubstituted spin probe, determined from an Arrhenius plot of the spin-probe mobility in the ionic liquid above the melting temperature, is comparable with the activation energy for the viscous flow of the ionic liquid, but is higher for spin probes bearing an additional substituent at the 4-position. Quantum chemical calculations of the spin probes using the 6-31G+d method give information about the rotational volume of the spin probes and the spin density at the nitrogen atom of the radical structure as a function of the substituent at the spin probes in the presence and absence of a counter ion. The results of these calculations help in understanding the effect of the additional substituent on the experimentally determined isotropic hyperfine coupling constant.}, language = {en} } @article{ThielZehbeRoesneretal.2013, author = {Thiel, Kerstin and Zehbe, Rolf and Roesner, Jer{\^o}m{\´e} and Strauch, Peter and Enthaler, Stephan and Thomas, Arne}, title = {A polymer analogous reaction for the formation of imidazolium and NHC based porous polymer networks}, doi = {10.1039/C2PY20947K}, year = {2013}, abstract = {A polymer analogous reaction was carried out to generate a porous polymeric network with N-heterocyclic carbenes (NHC) in the polymer backbone. Using a stepwise approach, first a polyimine network is formed by polymerization of the tetrafunctional amine tetrakis(4-aminophenyl)methane. This polyimine network is converted in the second step into polyimidazolium chloride and finally to a polyNHC network. Furthermore a porous Cu(II)-coordinated polyNHC network can be generated. Supercritical drying generates polymer networks with high permanent surface areas and porosities which can be applied for different catalytic reactions. The catalytic properties were demonstrated for example in the activation of CO2 or in the deoxygenation of sulfoxides to the corresponding sulfides.}, language = {en} } @article{KozlevcarKovscaJaglicicetal.2009, author = {Kozlevcar, Bojan and Kovsca, Igor and Jaglicic, Zvonko and Pevec, Andrej and Kitanovski, Nives and Strauch, Peter and Segedin, Primoz}, title = {Strong antiferromagnetism in isolated anionic dicopper(II) methanoato paddle-wheel complex}, issn = {0011-1643}, year = {2009}, language = {en} } @article{KozlevcarKovscaJaglicicetal.2009, author = {Kozlevcar, Bojan and Kovsca, Igor and Jaglicic, Zvonko and Pevec, Andrej and Kitanovski, Nives and Strauch, Peter and {\`e}egedin, Primož}, title = {Strong antiferromagnetism in isolated anionic dicopper(II) methanoato paddle-wheel complex}, issn = {0011-1643}, year = {2009}, abstract = {A new ionic compound (C5H6NO)(2)[CU2(mu-O2CH)(4)(O2CH)(2)], 1 formed of 4-hydroxypyridinium cations and a complex anion was synthesized. The anion is a paddle-wheel dicopper carboxylate complex with four syn,syn-bridging and two axial anionic methanoato ligands. The XRD structure determination of 1 reveals that the molecular structure is stabilized by two H-bonds between the cations and the axial paddle-wheel anions (N-H center dot center dot center dot O 2.755(3), O-H center dot center dot center dot O 2.489(2) angstrom). The compound exhibits a very strong (2J = 500 cm(- 1)) intra-binuclear anti ferromagnetic interaction noticed already at room temperature attributed to the methanoato intra-binuclear bridges. The typical EPR S = 1 spin system signals of the dicopper paddle-wheel complexes at 90 and 450- 700 mT are found in the room temperature spectrum, but they are poorly seen in the 110 K spectrum. These signals are of very low intensity and are accompanied by a dominant signal at 320 mT, all closely related to a very strong anti ferromagnetic interaction present in 1.}, language = {en} } @article{KozlevcarMateJaglicicetal.2009, author = {Kozlevcar, Bojan and Mate, Elizabeta and Jaglicic, Zvonko and Glažar, Lea and Golobic, Amalija and Strauch, Peter and Moncol, Jan and Kitanovski, Nives and {\`e}egedin, Primož}, title = {A small methanoato ligand in the structural differentiation of copper(II) complexes}, issn = {0277-5387}, doi = {10.1016/j.poly.2009.05.066}, year = {2009}, abstract = {Several copper(II) methanoato complexes, namely mononuclear [Cu(O2CH)(2)(2-mpy)(2)] (1) (2-mpy = 2- methylpyridine), binuclear [Cu-2(mu-O2CH)(4)(2-mpy)(2)] (2), and the polynuclear {[Cu(mu-O2CH)(2)(2-mpy)(2)] [Cu-2(mu- O2CH)(4)]}(n) (3) and {Na-2[Cu(mu-O2CH)(2)(O2CH)(2)][Cu-2(mu-O2CH)(4)]}(n) (4), have been synthesized. The mononuclear complex I is formed by two asymmetric chelate methanoate anions and two 2-methylpyridine molecules, giving a highly distorted 'elongated octahedral' coordination sphere. Complex I decomposes outside the mother-liquid, transforming into a regular isolated binuclear paddle-wheel complex 2 with four intra-binuclear bridging methanoates and two axial 2-mpy ligands. The polynuclear complex 3 is formed of alternate mononuclear and binuclear building blocks resembling the central cores of I and 2, but with significant differences, especially for the methanoates of the mononuclear units. The oxygen atom of the mononuclear unit in the octahedral axial position in 3 is simultaneously coordinated to the axial position of the binuclear paddle-wheel central core, thus enabling a chain type of structure. A chain of alternate mononuclear and binuclear building blocks, as in the neutral compound 3. are found as well in the ionic polymeric compound 4, though two types of bridges are found in 4, while there is only one type in 3. Namely, the axial position of the octahedral mononuclear unit in 4 is occupied by the methanoate oxygen atom that is already a part of the binuclear paddle-wheel unit, while one equatorial methanoate from the mononuclear unit serves as a triatomic bridge to the axial position of the binuclear building block. A very strong antiferromagnetic interaction is found for all the complexes with the paddle-wheel building blocks [Cu-2(mu-O2CH)(4)] 2-4 (-2J = 444-482 cm(-1)), attributed to the methanoate intra-binuclear bridges. On the other hand, this strong antiferromagnetism, found already at room temperature, reduces the intensity of the EPR S = 1 spin signals reported for the isolated paddle-wheel complex 2. For the polymeric 3, only the spin S = 1/2 signals are found in the EPR spectra, and they are assigned to the mononuclear building blocks. No signals with a clear origin are however seen in the room temperature EPR spectrum of the polymeric analogue 4, only the S = 1/2 signals in the low temperature spectra. This feature is suggested to be due to a specific influence between the adjacent S = 1 (binuclear) and S = 1/2 (mononuclear) species via their bridges.}, language = {en} } @article{HalaskaPevecStrauchetal.2013, author = {Halaska, Jozef and Pevec, Andrej and Strauch, Peter and Kozlevcar, Bojan and Koman, Marian and Moncol, Jan}, title = {Supramolecular hydrogen-bonding networks constructed from copper(II) chlorobenzoates with nicotinamide - Structure and EPR}, series = {Polyhedron : the international journal of inorganic and organometallic chemistry}, volume = {61}, journal = {Polyhedron : the international journal of inorganic and organometallic chemistry}, publisher = {Elsevier}, address = {Oxford}, issn = {0277-5387}, doi = {10.1016/j.poly.2013.05.032}, pages = {20 -- 26}, year = {2013}, abstract = {Nicotinamide (nia) has been employed as a supramolecular reagent in the synthesis of four copper(II) chloro- and dichlorobenzoate (Clbz/Cl(2)bz) complexes. The structures of the compounds [Cu(2-Clbz)(2) (nia)(2)(H2O)(2)] (1), icu(4-clbz)(2)(nia)(2)(H2O)(2)] (2), [Cu(3,5-Cl(2)bz)(2)(nia)(2)(H2O)(2)] (3), and [Cu(2,5-Cl(2)bz)(2) (nia)(2)(H2O)]center dot H2O (4) were determined. All the investigated compounds 1-4 reveal water molecules as coordinated. Their structures show distorted octahedral chromophores (CuN2O2O)-N-II'(2), though some are better described as square-planar or square-pyramid due to a large deviation of the axial ligand away from the octahedral z-axis along with different Cu center dot center dot center dot O (axial) lengths. The equatorial positions are occupied in all four cases by two nitrogen (nia-py) atoms and two carboxylate oxygen atoms of two Clbz/Cl(2)bz ligands, while the axial positions are occupied by water molecules. The EPR spectra reveal for all 1-4 compounds a spin state of S = 1/2, mostly with axial symmetry of the spectra. Their resolution is clearly dependant to the crystal symmetry related equivalence of the magnetic sites. The coordination molecules of all compounds are connected by N-H center dot center dot center dot O and O-H center dot center dot center dot O H-bonds from nicotinamide NH2 groups, carboxylate anions and/or water molecules, which create supramolecular chains or further H-bonded into 2D sheets. Steric hindering of the chlorine atoms of the Clbz/Cl(2)bz, especially seen at the coordination of the water molecules, demonstrates its role at the coordination sphere appearance. Despite this influence, the water molecules in 1-4 always assist at the similar supramolecular H-bonded network, almost at the same manner.}, language = {en} } @article{FischerSchmidtStrauchetal.2013, author = {Fischer, Sabrina and Schmidt, Johannes and Strauch, Peter and Thomas, Arne}, title = {An anionic microporous polymer network prepared by the polymerization of weakly coordinating anions}, series = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, volume = {52}, journal = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, number = {46}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1433-7851}, doi = {10.1002/anie.201303045}, pages = {12174 -- 12178}, year = {2013}, language = {en} } @article{SieboldKorabikSchildeetal.2008, author = {Siebold, Matthias and Korabik, Maria and Schilde, Uwe and Mrozinski, Jerzy and Strauch, Peter}, title = {Pentanuclear heterobimetallic 3d-4f complexes of Ln2M3-type - structure and magnetism}, issn = {0366-6352}, year = {2008}, abstract = {From a series of pentanuclear, heterobimetallic complexes of the general composition [{Ln(H2O)n}2{Ni(dto)2}3] · xH2O, four complexes (Ln = Gd(III) with n = 4; Ln = Dy(III), Ho(III), or Er(III), with n = 5; x = 9-12; dto = 1,2- dithiooxalate) were studied due to their large magnetic moments (up to 14.65 B.M.). The magnetic properties of these complete series were measured at room temperature and the temperature dependent magnetic properties of the complexes Gd2Ni3, Dy2Ni3, Ho2Ni3, and Er2Ni3 were studied at room temperature down to 1.8 K. Whereas the intramolecular metal- metal distances were rather long (Ni1-Ni2: 11.0-11.5 {\AA}; Ln-Ni: 6.0-6.3 {\AA}), relatively short intermolecular metal-metal distances (Ni1-Ni2;: 3.5 {\AA}; Er-Er;: 6.0 {\AA}) were found in the crystal lattice, giving rise to weak intermolecular metal-metal interactions. These weak spin interactions were also supported by the EPR spectrum of a powdered sample of the diamagnetically undiluted Gd2Ni3 complex.}, language = {en} } @article{AwadConradKochetal.2010, author = {Awad, Duha Jawad and Conrad, Franziska and Koch, Andreas and Friedrich, Alwin and Poeppl, Andreas and Strauch, Peter}, title = {2,2'-Bipyridin-1,2-dithiolat Gemischtligand-Komplexe : Systhese, Charakterisierung und EPR-Spektroskopie}, issn = {0932-0776}, year = {2010}, abstract = {A series of new 2 2'-bipyridine/1 2-dithiolate transition metal complexes has been synthesised and characterised As 1,2-dithiolate ligands 1,2 dithiooxalate (dto) and 1 2-dithiosquarate (dtsq) were used It follows from the IR spectra that the multidentate dithiolate ligands coordinate exclusively via their sulfur atoms forming an MN2S2 coordination sphere The central metal ions (M) are Cu2+ Ni2+ Pd2+ Pt2+, and Zn2+ The complex [Cu-II(bpy)(dto)] could be studied by EPR spectroscopy and was measured as powder diamagnetically diluted in the isostructural [Ni-II(bpy)(dto)] host structure The spin density contribution calculated from the experimental parameters is compared with the electronic situation in the frontier orbitals namely in the semi occupied SOMO of the copper complex derived from quantum chemical calculations on different levels (EHT and DFT)}, language = {de} } @article{AwadConradKochetal.2010, author = {Awad, Duha Jawad and Conrad, Franziska and Koch, Andreas and Schilde, Uwe and Poeppl, Andreas and Strauch, Peter}, title = {1,10-phenanthroline-dithiolate mixed ligand transition metal complexes : synthesis, characterization and EPR spectroscopy}, issn = {0020-1693}, doi = {10.1016/j.ica.2010.01.021}, year = {2010}, abstract = {A series of new N2S2 mixed ligand transition metal complexes, where N-2 is phenanthroline and S-2 is 1,2- dithiooxalate (dto) or 1,2-dithiosquarate (dtsq), has been synthesized and characterized. IR spectra reveal that the 1,2- dithiolate ligands are coordinated via the sulfur atoms forming a N2S2 coordination sphere. The copper(II) complex [Cu(phen)(dto)] was studied by EPR spectroscopy as a diamagnetically diluted powder. The diamagnetic dilution resulted from doping of the copper complex into the isostructural host lattice of the nickel complex [Ni(phen)(dto)]. The electronic situation in the frontier orbitals of the copper complex calculated from the experimental data is compared to the results of EHT and DFT calculations. Furthermore, one side product, chlorobis(1,10-phenanthroline)copper(I) ethanol solvate hydrate [(phen)(2)CuCl]center dot C2H5OH center dot H2O, was formed by a reduction process and characterized by X-ray diffraction. In the crystal packing one-dimensional columns of dimers are formed, stabilized by significant pi-pi interactions.}, language = {en} } @article{KozlevcarOdlazekGolobicetal.2006, author = {Kozlevcar, Bojan and Odlazek, Darja and Golobic, Amalija and Pevec, Andrej and Strauch, Peter and Segedin, Primoz}, title = {Complexes with lignin model compound vanillic acid : two different carboxylate ligands in the same dinuclear tetracarboxylate complex [Cu-2(C8H7O4)(2)(O2CCH3)(2)(CH3OH)(2)]}, issn = {0277-5387}, doi = {10.1016/j.poly.2005.08.031}, year = {2006}, abstract = {Two copper(II) coordination compounds with vanillic acid C8H8O4 (1), namely [Cu- 2(C8H7O4)(2)(O2CCH3)(2)(CH3OH)(2)] (2) and [Cu-2(C8H7O4)(4)(H2O2)(2)] (3), were synthesized and characterized. Single crystals of 1-3 were obtained and their crystal structures determined. The structure of 2 shows dinuclear cage structure of copper acetate hydrate type, however with two different carboxylates, acetates and vanillic acid anions,. respectively. Both bridging anions are in pairs in trans orientation. Methanol molecules are apically coordinated (Cu-O7 2.160(2) angstrom), fulfilling square-pyramidal coordination sphere around both copper ions. The compound 2 decomposes outside mother-liquid (yielding [Cu-2(C8H7O4)(2)(O2CCH3)(2)(H2O)(2)] (2a)) with the removal of methanol, but without significant change of the dicopper tetracarboxylate cage structure, as noticed by mu(eff) 1.48 BM for 2a. Similar was found also in the X-band EPR spectra with three signals H-z1, H-perpendicular to 2 and H-z2 in the region from 0 to 600 mT. The structure of free vanillic acid 1 is composed of dimeric units of two molecules, connected by two parallel hydrogen bonds between carboxylate group of each other (O1-H(...)O2 2.642(3) angstrom), while the structure of 3 is of [Cu-2(O2CCH3)(4)(H2O)(2)] type. Interestingly, an additional signal in the EPR spectra of 3 is found at 80 mT (H- perpendicular to 1) at 298 and at 116 K, next to three signals H-z1, H-perpendicular to 2 and H-z2.}, language = {en} } @article{AwadKochMickleretal.2012, author = {Awad, Duha Jawad and Koch, Andreas and Mickler, Wulfhard and Schilde, Uwe and Strauch, Peter}, title = {EPR spectroscopy of 4, 4 '-Bis(tert-butyl)-2, 2 '-bipyridine-1, 2-dithiolatocuprates(II) in host lattices with different coordination geometries}, series = {Zeitschrift f{\"u}r anorganische und allgemeine Chemie}, volume = {638}, journal = {Zeitschrift f{\"u}r anorganische und allgemeine Chemie}, number = {6}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0044-2313}, doi = {10.1002/zaac.201100517}, pages = {965 -- 975}, year = {2012}, abstract = {A series of new heteroleptic MN2S2 transition metal complexes with M = Cu2+ for EPR measurements and as diamagnetic hosts Ni2+, Zn2+, and Pd2+ were synthesized and characterized. The ligands are N2 = 4, 4'-bis(tert-butyl)-2, 2'-bipyridine (tBu2bpy) and S2 =1, 2-dithiooxalate, (dto), 1, 2-dithiosquarate, (dtsq), maleonitrile-1, 2-dithiolate, or 1, 2-dicyanoethene-1, 2-dithiolate, (mnt). The CuII complexes were studied by EPR in solution and as powders, diamagnetically diluted in the isostructural planar [NiII(tBu2bpy)(S2)] or[PdII(tBu2bpy)(S2)] as well as in tetrahedrally coordinated[ZnII(tBu2bpy)(S2)] host structures to put steric stress on the coordination geometry of the central CuN2S2 unit. The spin density contributions for different geometries calculated from experimental parameters are compared with the electronic situation in the frontier orbital, namely in the semi-occupied molecular orbital (SOMO) of the copper complex, derived from quantum chemical calculations on different levels (EHT and DFT). One of the hosts, [NiII(tBu2bpy)(mnt)], is characterized by X-ray structure analysis to prove the coordination geometry. The complex crystallizes in a square-planar coordination mode in the monoclinic space group P21/a with Z = 4 and the unit cell parameters a = 10.4508(10) angstrom, b = 18.266(2) angstrom, c = 12.6566(12) angstrom, beta = 112.095(7)degrees. Oxidation and reductions potentials of one of the host complexes, [Ni(tBu2bpy)(mnt)], were obtained by cyclovoltammetric measurements.}, language = {en} } @article{StrehmelRexhausenStrauch2012, author = {Strehmel, Veronika and Rexhausen, Hans and Strauch, Peter}, title = {New spin probes starting from 4-amino-2,2,6,6-tetramethylpiperidine-1-yloxyl}, series = {Tetrahedron letters}, volume = {53}, journal = {Tetrahedron letters}, number = {13}, publisher = {Elsevier}, address = {Oxford}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2012.01.063}, pages = {1587 -- 1591}, year = {2012}, abstract = {This Letter describes four new 4-trimethylammonio-2,2,6,6-tetramethylpiperidine-1-yloxyls bearing camphorsulfonate, triflate, tosylate, or lactate as counter ions. These spin probes were made by anion metathesis of 4-trimethylammonio-2,2,6,6-tetramethylpiperidine-1-yloxyl iodide using the corresponding silver salts. The latter is made by the alkylation of 4-amino-2,2,6,6-tetramethylpiperidine-1-yloxyl. Furthermore, the Letter gives an improved synthetic way to 4-sulfonamido-2,2,6,6-tetramethylpiperidine-1-yloxyl using chlorosulfuric acid trimethylsilylester and 4-amino-2,2,6,6-tetramethylpiperidine-1-yloxyl. All the spin probes are highly interesting for the investigation of ionic liquids.}, language = {en} } @article{KozlevcarGamezdeGelderetal.2011, author = {Kozlevcar, Bojan and Gamez, Patrick and de Gelder, Rene and Jaglicic, Zvonko and Strauch, Peter and Kitanovski, Nives and Reedijk, Jan}, title = {Counterion and solvent effects on the primary coordination sphere of copper(II) Bis(3,5-dimethylpyrazol-1-yl)acetic acid coordination compounds}, series = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, journal = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, number = {24}, publisher = {Wiley-Blackwell}, address = {Malden}, issn = {1434-1948}, doi = {10.1002/ejic.201100410}, pages = {3650 -- 3655}, year = {2011}, abstract = {Four copper(II) coordination compounds with the neutral ligand bis(3,5-dimethylpyrazol-1-yl)acetic acid (Hbdmpza, C(12)H(16)N(4)O(2)) and its anionic form (bdmpza(-)), namely [Cu(Hbdmpza)(2)](HSO(4))(2) (1), [Cu(Hbdmpza)(2)]Cl(2) (2), [Cu(bdmpza)(2)](CH(3)COOH)(H(2)O) (3), and [Cu(bdmpza)(2)][Cu(2)(O(2)CCH(3))(4)] (4) have been synthesized starting from different metal salts. All the compounds have been fully characterized by physical and analytical methods. In addition, a single-crystal XRD analysis revealed the 3D structure of 1, which exhibits tridentate, vicinal N,N,O-coordination of two symmetry-related Hbdmpza ligands in an elongated octahedral arrangement with four equatorial nitrogen atoms and two axial oxygen atoms. The neutral carboxylic moiety acts as a hydrogen-bond donor to a HSO(4)(-) counterion. The two hydrogensulfates form a unique hydrogen-bonded pair (HSO(4)(-))(2) with very short O center dot center dot center dot O distances (2.59 angstrom) bridged between adjacent [Cu(HL)(2)](2+) coordination units. Also a short O center dot center dot center dot O contact (2.54 angstrom) is present between the C-OH and an 0 of a hydrogensulfate. A characteristic IR C=O vibration is observed at 1700 cm(-1) for 1 and 2, whereas the v(as)(O(2)C) vibration is present at 1650 cm(-1) for 3 and 4. These IR data strongly suggest the presence of Hbdmpza ligands in 1 and 2 and the deprotonated form bdmpza- in 3 and 4. A mononuclear coordination unit [CuL(2)], as proven for 1 by X-ray diffraction, is also proposed for the other compounds 2-4. In compound 4, an additional dinuclear [Cu(2)(O(2)CCH(3))(4)] neutral coordination unit is present, as deduced from the vibration bands v(as)(O(2)C) at 1600 cm(-1) and v(s)(O(2)C) at 1420 cm(-1), which are typical of a carboxylate function, and from the two-species analysis of the chi(M)T(T) curve of the magnetic susceptibility data (2J = -322 cm(-1)). Also, the EPR spectra recorded at different temperatures agree with this structure.}, language = {en} } @article{VaskovaKitanovskiJaglicicetal.2014, author = {Vaskova, Zuzana and Kitanovski, Nives and Jaglicic, Zvonko and Strauch, Peter and Ruzickova, Zdenka and Valigura, Dusan and Koman, Marian and Kozlevcar, Bojan and Moncol, Jan}, title = {Synthesis and magneto-structural characterization of copper(II) nitrobenzoate complexes containing nicotinamide or methylnicotinamide ligands}, series = {Polyhedron : the international journal of inorganic and organometallic chemistry}, volume = {81}, journal = {Polyhedron : the international journal of inorganic and organometallic chemistry}, publisher = {Elsevier}, address = {Oxford}, issn = {0277-5387}, doi = {10.1016/j.poly.2014.07.017}, pages = {555 -- 563}, year = {2014}, abstract = {Three new copper(II) 4-nitrobenzoato coordination compounds (4-NO(2)bz(-) = 4-nitrobenzoate anions) with N-methylnicotinamide (mna) [Cu(4-NO(2)bz)(2)(mna)(2)(H2O)] (1), [Cu(4-NO(2)bz)(2)(mu-mna)(H2O)](2) (2) and [Cu(mu-4-NO(2)bz)(2)(mna)](2) (3) were synthesized and characterized. Due to a comparison, additional two related compounds [Cu(3,5-(NO2)(2)bz)(2)(mna)(2)(H2O)] (4) (nia = nicotinamide, 3,5-(NO2)(2)bz(-) = 3,5-dinitrobenzoate anions) and [Cu(mu-2-NO(2)bz)(2)(mna)](2) (5) (2-NO(2)bz(-) = 2-nitrobenzoate anions) were isolated. The mononuclear compounds with mna 1 and nia 4 show CuO2N2O chromophores with the water molecule placed at the apex of the square pyramid. The square-pyramidal coordination sphere CuO3NO in 2 differs to CuO2N2O in 1 and 4. Differently, the water molecule is in 2 at the basal-plane, while two mna molecules serve also as bridges via N-py and 0-amido enabling a dinuclear molecular structure 1, 2 and 4 are paramagnetic though a dinuclear structure is seen in 2, while a clear-cut strong antiferromagnetic (AFM) coupling (2J -300 cm(-1)) is found for the compounds 3 and 5. (C) 2014 Elsevier Ltd. All rights reserved.}, language = {en} } @article{BaumgartnerLesevicKumarietal.2012, author = {Baumgartner, Jens and Lesevic, Paul and Kumari, Monika and Halbmair, Karin and Bennet, Mathieu and Koernig, Andre and Widdrat, Marc and Andert, Janet and Wollgarten, Markus and Bertinetti, Luca and Strauch, Peter and Hirt, Ann and Faivre, Damien}, title = {From magnetotactic bacteria to hollow spirilla-shaped silica containing a magnetic chain}, series = {RSC Advances}, volume = {2}, journal = {RSC Advances}, number = {21}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2046-2069}, doi = {10.1039/c2ra20911j}, pages = {8007 -- 8009}, year = {2012}, abstract = {Magnetotactic bacteria produce chains of magnetite nanoparticles, which are called magnetosomes and are used for navigational purposes. We use these cells as a biological template to prepare a hollow hybrid material based on silica and magnetite, and show that the synthetic route is nondestructive as the material conserves the cell morphology as well as the alignment of the magnetic particles. The hybrid material can be resuspended in aqueous solution, and can be shown to orient itself in an external magnetic field. We anticipate that chemical modification of the silica can be used to functionalize the material surface in order to obtain multifunctional materials with specialized applications, e.g. targeted drug delivery.}, language = {en} } @article{NajafpourHillierShamkhalietal.2012, author = {Najafpour, Mohammad Mahdi and Hillier, Warwick and Shamkhali, Amir Nasser and Amini, Mojtaba and Beckmann, Katrin and Jaglicic, Zvonko and Jagodic, Marko and Strauch, Peter and Moghaddam, Atefeh Nemati and Beretta, Giangiacomo and Bagherzadeh, Mojtaba}, title = {Synthesis, characterization, DFT studies and catalytic activities of manganese(II) complex with 1,4-bis(2,2 ':6,2 ''-terpyridin-4 '-yl) benzene}, series = {Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry}, volume = {41}, journal = {Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry}, number = {39}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1477-9226}, doi = {10.1039/c2dt31544k}, pages = {12282 -- 12288}, year = {2012}, abstract = {A new di-manganese complex with "back-to-back" 1,4-bis(2,2':6,2 ''-terpyridin-4'-yl) benzene ligation has been synthesized and characterised by a variety of techniques. The back-to-back ligation presents a novel new mononuclear manganese catalytic centre that functions as a heterogeneous catalysis for the evolution of oxygen in the presence of an exogenous oxidant. We discuss the synthesis and spectroscopic characterizations of this complex and propose a mechanism for oxygen evolution activity of the compound in the presence of oxone. The di-manganese complex also shows efficient and selective catalytic oxidation of sulfides in the presence of H2O2. Density functional theory calculations were used to assess the structural optimization of the complex and a proposed reaction pathway with oxone. The calculations show that middle benzene ring is distorted respect to both of metallic centers, and this in turn leads to negligible resonance of electrons between two sides of complex. The calculations also indicate the unpaired electron located on oxyl-ligand emphasizes the radical mechanism of water oxidation for the system.}, language = {en} } @article{SchmittWinterBertinettietal.2015, author = {Schmitt, Clemens Nikolaus Zeno and Winter, Alette and Bertinetti, Luca and Masic, Admir and Strauch, Peter and Harrington, Matthew J.}, title = {Mechanical homeostasis of a DOPA-enriched biological coating from mussels in response to metal variation}, series = {Interface : journal of the Royal Society}, volume = {12}, journal = {Interface : journal of the Royal Society}, number = {110}, publisher = {Royal Society}, address = {London}, issn = {1742-5689}, doi = {10.1098/rsif.2015.0466}, pages = {8}, year = {2015}, abstract = {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.}, language = {en} } @article{NeumannNoeskeBachetal.2011, author = {Neumann, Mike and Noeske, Robert and Bach, Grete and Glaubauf, Thomas and Bartoszek, Michael and Strauch, Peter}, title = {A procedure for rapid determination of the silicon content in plant materials}, series = {Zeitschrift f{\"u}r Naturforschung : B, Chemical sciences}, volume = {66}, journal = {Zeitschrift f{\"u}r Naturforschung : B, Chemical sciences}, number = {3}, publisher = {De Gruyter}, address = {T{\"u}bingen}, issn = {0932-0776}, pages = {289 -- 294}, year = {2011}, abstract = {An efficient, reliable and low-cost procedure to determine the silicon content in plant material is presented which allows to monitor the agricultural aspects like growth and yield. The presented procedure consists of a hydrochloric acid pre-treatment and a subsequent thermal oxidation. The method is compared to other processes like dissolution in hydrofluoric acid combined with ICP OES, energy-dispersive X-ray fluorescence spectroscopy (EDXRF) or aqua regia treatment.}, language = {en} } @article{StrehmelBerdzinskiStrauchetal.2014, author = {Strehmel, Veronika and Berdzinski, Stefan and Strauch, Peter and Hoffmann-Jacobsen, Kerstin and Strehmel, Bernd}, title = {Investigation of molecular solvents and ionic liquids with a dual probe}, series = {Zeitschrift f{\"u}r physikalische Chemie : international journal of research in physical chemistry and chemical physics}, volume = {228}, journal = {Zeitschrift f{\"u}r physikalische Chemie : international journal of research in physical chemistry and chemical physics}, number = {2-3}, publisher = {De Gruyter}, address = {Berlin}, issn = {0942-9352}, doi = {10.1515/zpch-2014-0453}, pages = {155 -- 169}, year = {2014}, abstract = {A dual probe was investigated by UV-Vis, fluorescence, and ESR spectroscopy. It comprises the pyrene chromophore and the paramagnetic 2,2,6,6-tetramethylpiperidinyl-N-oxyl radical that are covalently linked together via an ester bridge. The dual probe was used to investigate molecular solvents of different polarity as well as ionic liquids bearing either imidazolium or pyrrolidinium cations and various anions, such as bis(trifluoromethylsulfonyl)imide, tetrafluoroborate, tris(pentafluoroethyl)trifluorophosphate, or dicyanamide. The dual probe does not show solvatochromism that is typical for some pyrenes. Furthermore, the dual probe is considerable less mobile compared to 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO) without additional substituent as detected by ESR spectroscopy. This is caused by the bulky pyrenyl substituent bound at the dual probe resulting in a reduced mobility of the dual probe.}, language = {en} } @article{ThielZehbeRoeseretal.2013, author = {Thiel, Kerstin and Zehbe, Rolf and R{\"o}ser, Jerome and Strauch, Peter and Enthaler, Stephan and Thomas, Arne}, title = {A polymer analogous reaction for the formation of imidazolium and NHC based porous polymer networks}, series = {Polymer Chemistry}, volume = {4}, journal = {Polymer Chemistry}, number = {6}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1759-9954}, doi = {10.1039/c2py20947k}, pages = {1848 -- 1856}, year = {2013}, abstract = {A polymer analogous reaction was carried out to generate a porous polymeric network with N-heterocyclic carbenes (NHC) in the polymer backbone. Using a stepwise approach, first a polyimine network is formed by polymerization of the tetrafunctional amine tetrakis(4-aminophenyl)methane. This polyimine network is converted in the second step into polyimidazolium chloride and finally to a polyNHC network. Furthermore a porous Cu(II)-coordinated polyNHC network can be generated. Supercritical drying generates polymer networks with high permanent surface areas and porosities which can be applied for different catalytic reactions. The catalytic properties were demonstrated for example in the activation of CO2 or in the deoxygenation of sulfoxides to the corresponding sulfides.}, language = {en} } @article{WinterZabelStrauch2012, author = {Winter, Alette and Zabel, Andre and Strauch, Peter}, title = {Tetrachloridocuprates(II)-Synthesis and Electron Paramagnetic Resonance (EPR) Spectroscopy}, series = {International journal of molecular sciences}, volume = {13}, journal = {International journal of molecular sciences}, number = {2}, publisher = {MDPI}, address = {Basel}, issn = {1661-6596}, doi = {10.3390/ijms13021612}, pages = {1612 -- 1619}, year = {2012}, abstract = {Ionic liquids (ILs) on the basis of metal containing anions and/or cations are of interest for a variety of technical applications e.g., synthesis of particles, magnetic or thermochromic materials. We present the synthesis and the results of electron paramagnetic resonance (EPR) spectroscopic analyses of a series of some new potential ionic liquids based on tetrachloridocuprates(II), [CuCl4](2-), with different sterically demanding cations: hexadecyltrimethylammonium 1, tetradecyltrimethylammonium 2, tetrabutylammonium 3 and benzyltriethylammonium 4. The cations in the new compounds were used to achieve a reasonable separation of the paramagnetic Cu(II) ions for EPR spectroscopy. The EPR hyperfine structure was not resolved. This is due to the exchange broadening, resulting from still incomplete separation of the paramagnetic Cu(II) centers. Nevertheless, the principal values of the electron Zeemann tensor (g parallel to and g perpendicular to) of the complexes could be determined. Even though the solid substances show slightly different colors, the UV/Vis spectra are nearly identical, indicating structural changes of the tetrachloridocuprate moieties between solid state and solution. The complexes have a promising potential e.g., as high temperature ionic liquids, as precursors for the formation of copper chloride particles or as catalytic paramagnetic ionic liquids.}, language = {en} } @article{AwadSchildeStrauch2011, author = {Awad, Duha Jawad and Schilde, Uwe and Strauch, Peter}, title = {4,4 '-Bis(tert-butyl)-2,2 '-bipyridinedichlorometal(II) - Synthesis, structure and EPR spectroscopy}, series = {Inorganica chimica acta : the international inorganic chemistry journal}, volume = {365}, journal = {Inorganica chimica acta : the international inorganic chemistry journal}, number = {1}, publisher = {Elsevier}, address = {Lausanne}, issn = {0020-1693}, doi = {10.1016/j.ica.2010.08.035}, pages = {127 -- 132}, year = {2011}, abstract = {Due to the better solubility of the 4,4'-substituted bipyridine ligand a series of 4,4'0-bis(tert-butyl)-2,2'-bipyridinedichlorometal(II) complexes, [M(tbbpy)Cl(2)], with M = Cu, Ni, Zn, Pd, Pt was synthesised and characterised. The blue copper complex 4,4'-bis(tert-butyl)-2,2'-bipyridinedichlorocopper(II) was isolated in two different polymorphic forms, as prisms 1 with a solvent inclusion and solvent-free as needles 2. Both structures were determined by X-ray structure analysis. They crystallise in the monoclinic space group P2(1)/c with four molecules in the unit cell, but with different unit cells and packing motifs. Whereas in the prisms 1, with the unit cell parameters a = 12.1613(12), b = 10.6363(7), c = 16.3074(15) angstrom, eta = 94.446(8)degrees, the packing is dominated by intra-and intermolecular hydrogen bonds, in the needles 2, with a = 7.738(1), b = 18. 333(2), c = 13.291(3) angstrom, beta = 97.512(15)degrees, only intramolecular hydrogen bonds appear and the complex molecules are arranged in columns which are stabilised by p-p-stacking interactions. In both complexes the copper has a tetrahedrally distorted coordination sphere. These copper complexes were also studied by EPR spectroscopy in solution, as frozen glass and diamagnetically diluted powder with the analogue [Pd(tbbpy)Cl(2)] as host lattice.}, language = {en} } @article{StrauchKossmannKellingetal.2016, author = {Strauch, Peter and Kossmann, Alexander and Kelling, Alexandra and Schilde, Uwe}, title = {EPR on bis(1,2-dithiosquarato)cuprate(II) in the bis(1,2-dithiosquarato)nickelate(II) host lattice - structure and spectroscopy}, series = {Chemical papers}, volume = {70}, journal = {Chemical papers}, publisher = {De Gruyter}, address = {Berlin}, issn = {0366-6352}, doi = {10.1515/chempap-2015-0154}, pages = {61 -- 68}, year = {2016}, abstract = {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}, language = {en} } @article{ZabelWinterKellingetal.2016, author = {Zabel, Andre and Winter, Alette and Kelling, Alexandra and Schilde, Uwe and Strauch, Peter}, title = {Tetrabromidocuprates(II)-Synthesis, Structure and EPR}, series = {International journal of molecular sciences}, volume = {17}, journal = {International journal of molecular sciences}, publisher = {MDPI}, address = {Basel}, issn = {1422-0067}, doi = {10.3390/ijms17040596}, pages = {14}, year = {2016}, abstract = {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.}, language = {en} } @misc{KoenigKellingSchildeetal.2017, author = {K{\"o}nig, Jana and Kelling, Alexandra and Schilde, Uwe and Strauch, Peter}, title = {[µ2-O,O′,Oʺ,Oʺ′-Bis(1,2-dithiooxalato-S,S′)nickel(II)]bis[-O,O′-bis(1,2-dithiooxalato-S,S′)-nickel(II)pentaquaholmium(III)]hydrate, [Ho2Ni3(dto)6(H2O)10]}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-400598}, pages = {5}, year = {2017}, abstract = {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.}, language = {en} } @article{StrauchNeumannKellingetal.2015, author = {Strauch, Peter and Neumann, Mike and Kelling, Alexandra and Schilde, Uwe}, title = {Bis(1,2-dithiosquarato)nickelates(II): Synthesis, Structure, EPR and Thermal Behavior}, series = {Acta chimica Slovenica}, volume = {62}, journal = {Acta chimica Slovenica}, number = {2}, publisher = {Drustvo}, address = {Ljubljana}, issn = {1318-0207}, pages = {288 -- 296}, year = {2015}, abstract = {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.}, language = {en} } @article{GuelzowHoernerStrauchetal.2017, author = {Guelzow, Jana and Hoerner, Gerald and Strauch, Peter and Stritt, Anika and Irran, Elisabeth and Grohmann, Andreas}, title = {Oxygen Delivery as a Limiting Factor in Modelling Dicopper(II) Oxidase Reactivity}, series = {Chemistry - a European journal}, volume = {23}, journal = {Chemistry - a European journal}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201605868}, pages = {7009 -- 7023}, year = {2017}, abstract = {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.}, language = {en} } @article{KozlevcarGolobicStrauch2006, author = {Kozlevcar, Bojan and Golobic, Amalija and Strauch, Peter}, title = {Dynamic pseudo Jahn-Teller distortion in a compressed octahedral CuO6 complex}, series = {Polyhedron : the international journal of inorganic and organometallic chemistry}, volume = {25}, journal = {Polyhedron : the international journal of inorganic and organometallic chemistry}, number = {15}, publisher = {Elsevier}, address = {Oxford}, issn = {0277-5387}, doi = {10.1016/j.poly.2006.04.009}, pages = {2824 -- 2828}, year = {2006}, abstract = {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.}, language = {en} } @article{SeckerBrosnanLimbergetal.2015, author = {Secker, Christian and Brosnan, Sarah M. and Limberg, Felix Rolf Paul and Braun, Ulrike and Trunk, Matthias and Strauch, Peter and Schlaad, Helmut}, title = {Thermally Induced Crosslinking of Poly(N-Propargyl Glycine)}, series = {Macromolecular chemistry and physics}, volume = {216}, journal = {Macromolecular chemistry and physics}, number = {21}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1352}, doi = {10.1002/macp.201500223}, pages = {2080 -- 2085}, year = {2015}, abstract = {As polypeptoids become increasingly popular, they present a more soluble and processable alternative to natural and synthetic polypeptides; the breadth of their potential functionality slowly comes into focus. This report analyzes the ability of an alkyne-functionalized polypeptoid, poly(N-propargyl glycine), to crosslink upon heating. The crosslinking process is analyzed by thermal analysis (differential scanning calorimetry and thermogravimetric analysis), Fourier-transform infrared, electron paramagnetic resonance, and solid-state NMR spectroscopy. While a precise mechanism cannot be confidently assigned, it is clear that the reaction proceeds by a radical mechanism that exclusively involves the alkyne functionality, which, upon crosslinking, yields alkene and aromatic products.}, language = {en} } @article{SchwarzeKellingMuelleretal.2012, author = {Schwarze, Thomas and Kelling, Alexandra and M{\"u}ller, Holger and Trautmann, Michael and Klamroth, Tillmann and Baumann, Otto and Strauch, Peter and Holdt, Hans-J{\"u}rgen}, title = {N-2-Pyridinylmethyl-N '-arylmethyl-diaminomaleonitriles: New Highly Selective Chromogenic Chemodosimeters for Copper(II)}, series = {Chemistry - a European journal}, volume = {18}, journal = {Chemistry - a European journal}, number = {34}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201201731}, pages = {10506 -- 10510}, year = {2012}, language = {en} } @article{SonnenburgAdelhelmAntoniettietal.2006, author = {Sonnenburg, Kirstin and Adelhelm, Philipp and Antonietti, Markus and Smarsly, Bernd and N{\"o}ske, Robert and Strauch, Peter}, title = {Synthesis and characterization of SiC materials with hierarchical porosity obtained by replication techniques}, doi = {10.1039/B604819F}, year = {2006}, abstract = {Porous silicon carbide monoliths were obtained using the infiltration of preformed SiO2 frameworks with appropriate carbon precursors such as mesophase pitch. The initial SiO2 monoliths possessed a hierarchical pore system, composed of an interpenetrating bicontinuous macropore structure and 13 nm mesopores confined in the macropore walls. After carbonization, further heat treatment at ca. 1400 degrees C resulted in the formation of a SiC-SiO2 composite, which was converted into a porous SiC monolith by post-treatment with ammonium fluoride solution. The resulting porous SiC featured high crystallinity, high chemical purity and showed a surface area of 280 m(2) g(-1) and a pore volume of 0.8 ml g(-1)}, language = {en} } @misc{ThielZehbeRoeseretal.2013, author = {Thiel, Kerstin and Zehbe, Rolf and Roeser, Jer{\^o}m{\´e} and Strauch, Peter and Enthaler, Stephan and Thomas, Arne}, title = {A polymer analogous reaction for the formation of imidazolium and NHC based porous polymer networks}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-95118}, pages = {1848 -- 1856}, year = {2013}, abstract = {A polymer analogous reaction was carried out to generate a porous polymeric network with N-heterocyclic carbenes (NHC) in the polymer backbone. Using a stepwise approach, first a polyimine network is formed by polymerization of the tetrafunctional amine tetrakis(4-aminophenyl)methane. This polyimine network is converted in the second step into polyimidazolium chloride and finally to a polyNHC network. Furthermore a porous Cu(II)-coordinated polyNHC network can be generated. Supercritical drying generates polymer networks with high permanent surface areas and porosities which can be applied for different catalytic reactions. The catalytic properties were demonstrated for example in the activation of CO2 or in the deoxygenation of sulfoxides to the corresponding sulfides.}, language = {en} } @article{AbouserieZehbeMetzneretal.2017, author = {Abouserie, Ahed and Zehbe, Kerstin and Metzner, Philipp and Kelling, Alexandra and G{\"u}nter, Christina and Schilde, Uwe and Strauch, Peter and K{\"o}rzd{\"o}rfer, Thomas and Taubert, Andreas}, title = {Alkylpyridinium Tetrahalidometallate Ionic Liquids and Ionic Liquid Crystals: Insights into the Origin of Their Phase Behavior}, series = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, journal = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-1948}, doi = {10.1002/ejic.201700826}, pages = {5640 -- 5649}, year = {2017}, abstract = {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.}, language = {en} } @article{AbouserieZehbeMetzneretal.2017, author = {Abouserie, Ahed and Zehbe, Kerstin and Metzner, Philipp and Kelling, Alexandra and G{\"u}nter, Christina and Schilde, Uwe and Strauch, Peter and K{\"o}rzd{\"o}rfer, Thomas and Taubert, Andreas}, title = {Alkylpyridinium Tetrahalidometallate Ionic Liquids and Ionic Liquid Crystals: Insights into the Origin of Their Phase Behavior}, series = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, journal = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-1948}, doi = {10.1002/ejic.201700826}, pages = {5640 -- 5649}, year = {2017}, abstract = {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.}, language = {en} } @article{AyiKhareStrauchetal.2010, author = {Ayi, Ayi A. and Khare, Varsha and Strauch, Peter and Girard, J{\`e}r{\^o}me and Fromm, Katharina M. and Taubert, Andreas}, title = {On the chemical synthesis of titanium nanoparticles from ionic liquids}, issn = {0026-9247}, doi = {10.1007/s00706-010-0403-4}, year = {2010}, abstract = {We report on attempts towards the synthesis of titanium nanoparticles using a wet chemical approach in imidazolium-based ionic liquids (ILs) under reducing conditions. Transmission electron microscopy finds nanoparticles in all cases. UV/Vis spectroscopy confirms the nanoparticulate nature of the precipitate, as in all cases an absorption band between ca. 280 and 300 nm is visible. IR spectroscopy shows that even after extensive washing and drying, some IL remains adsorbed on the nanoparticles. Raman spectroscopy suggests the formation of anatase nanoparticles, but X-ray diffraction reveals that, possibly, amorphous titania forms or that the nanoparticles are so small that a clear structure assignment is not possible. The report thus shows that (possibly amorphous) titanium oxides even form under reducing conditions and that the chemical synthesis of titanium nanoparticles in ILs remains elusive.}, language = {en} } @article{NeumannNoeskeTaubertetal.2012, author = {Neumann, Mike and Noeske, Robert and Taubert, Andreas and Tiersch, Brigitte and Strauch, Peter}, title = {Highly structured, biomorphous beta-SiC with high specific surface area from Equisetaceae}, series = {Journal of materials chemistry}, volume = {22}, journal = {Journal of materials chemistry}, number = {18}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {0959-9428}, doi = {10.1039/c2jm30253e}, pages = {9046 -- 9051}, year = {2012}, abstract = {Mesoporous, highly structured silicon carbide (beta-SiC) was synthesised from renewable plant materials (two Equisetaceae species) in a one-step carbothermal process at remarkably low temperatures down to 1200 degrees C. The SiC precursor is a silicon-carbon mixture with finely dispersed carbon prepared by pyrolysis of the organic plant matrix. Yields are 3 to 100\% (omega(Si/Si) related to the silicon deposited in the plant material), depending on reaction temperature and time. IR spectroscopy, X-ray diffraction, and nitrogen sorption prove the formation of high-purity beta-SiC with minor inorganic impurities after purification and a high specific surface area of up to 660 m(2) g(-1). Scanning electron microscopy shows that the plant morphology is maintained in the final SiC. Sedimentation analysis finds a mean particle size (diameters d(50)) of 20 mu m.}, language = {en} } @article{FarraThielWinteretal.2011, author = {Farra, Ramzi and Thiel, Kerstin and Winter, Alette and Klamroth, Tillmann and Poeppl, Andreas and Kelling, Alexandra and Schilde, Uwe and Taubert, Andreas and Strauch, Peter}, title = {Tetrahalidocuprates(II)-structure and EPR spectroscopy Part 1: Tetrabromidocuprates(II)}, series = {New journal of chemistry}, volume = {35}, journal = {New journal of chemistry}, number = {12}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1144-0546}, doi = {10.1039/c1nj20271e}, pages = {2793 -- 2803}, year = {2011}, abstract = {Tetrahalidocuprates(II) show a high degree of structural flexibility. We present the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of four new tetrabromidocuprate(II) compounds and compare the results with previously reported data. The cations in the new compounds are the sterically demanding benzyltriphenylphosphonium, methyltriphenylphosphonium, tetraphenylphosphonium, and hexadecyltrimethylammonium ions; they were used to achieve a reasonable separation of the paramagnetic Cu(II) ions for EPR spectroscopy. X-Ray crystallography shows that in all four complexes the [CuBr4](2-) units have a distorted tetrahedral coordination geometry which is in agreement with DFT calculations. The EPR hyperfine structure was not resolved. This is due to the exchange broadening resulting from still incomplete separation of the paramagnetic Cu(II) centres. Nevertheless, the principal values of the electron Zeemann tensor (g(parallel to) and g(perpendicular to)) of the complexes could be determined. A correlation of structural (X-ray) parameters with the spin density at the copper centres (DFT) is well reflected in the EPR spectra of the bromidocuprates. This enables the correlation of X-ray and EPR parameters to predict the structure of tetrabromidocuprates in physical states other than the crystalline state. As a result, we provide a method to structurally characterize [CuBr4](2-) in, for example, ionic liquids or in solution, which has important implications for e.g. catalysis or materials science.}, language = {en} } @article{ThielKlamrothStrauchetal.2011, author = {Thiel, Kerstin and Klamroth, Tillmann and Strauch, Peter and Taubert, Andreas}, title = {On the interaction of ascorbic acid and the tetrachlorocuprate ion [CuCl4](2-) in CuCl nanoplatelet formation from an ionic liquid precursor (ILP)}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {13}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, number = {30}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/c1cp20648f}, pages = {13537 -- 13543}, year = {2011}, abstract = {The formation of CuCl nanoplatelets from the ionic liquid precursor (ILP) butylpyridinium tetrachlorocuprate [C4Py](2)[CuCl4] using ascorbic acid as a reducing agent was investigated. In particular, electron paramagnetic resonance (EPR) spectroscopy was used to evaluate the interaction between ascorbic acid and the Cu(II) ion before reduction to Cu(I). EPR spectroscopy suggests that the [CuCl4](2-) ion in the neat IL is a distorted tetrahedron, consistent with DFT calculations. Addition of ascorbic acid leads to the removal of one chloride from the [CuCl4](2-) anion, as shown by DFT and the loss of symmetry by EPR. DFT furthermore suggests that the most stable adduct is formed when only one hydroxyl group of the ascorbic acid coordinates to the Cu(II) ion.}, language = {en} } @article{WinterThielZabeletal.2014, author = {Winter, Alette and Thiel, Kerstin and Zabel, Andre and Klamroth, Tillmann and Poeppl, Andreas and Kelling, Alexandra and Schilde, Uwe and Taubert, Andreas and Strauch, Peter}, title = {Tetrahalidocuprates(II) - structure and EPR spectroscopy. Part 2: tetrachloridocuprates(II)}, series = {New journal of chemistry}, volume = {38}, journal = {New journal of chemistry}, number = {3}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1144-0546}, doi = {10.1039/c3nj01039b}, pages = {1019 -- 1030}, year = {2014}, abstract = {We present and discuss the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of five tetrachloridocuprate(II) complexes to supply a useful tool for the structural characterisation of the [CuCl4](2-) moiety in the liquid state, for example in ionic liquids, or in solution. Bis(benzyltriethylammonium)-, bis(trimethylphenylammonium)-, bis(ethyltriphenylphosphonium)-, bis(benzyltriphenylphosphonium)-, and bis(tetraphenylarsonium) tetrachloridocuprate(II) were synthesised and characterised by elemental, IR, EPR and X-ray analyses. The results of the crystallographic analyses show distorted tetrahedral coordination geometry of all [CuCl4](2-) anions in the five complexes and prove that all investigated complexes are stabilised by hydrogen bonds of different intensities. Despite the use of sterically demanding ammonium, phosphonium and arsonium cations to obtain the separation of the paramagnetic Cu(II) centres for EPR spectroscopy no hyperfine structure was observed in the EPR spectra but the principal values of the electron Zeeman tensor, g(parallel to) and g(perpendicular to), could be determined. With these EPR data and the crystallographic parameters we were able to carry out a correlation study to anticipate the structural situation of tetrachloridocuprates in different physical states. This correlation is in good agreement with DFT calculations.}, language = {en} } @misc{WinterThielZabeletal.2013, author = {Winter, Alette and Thiel, Kerstin and Zabel, Andr{\´e} and Klamroth, Tillmann and P{\"o}ppl, Andreas and Kelling, Alexandra and Schilde, Uwe and Taubert, Andreas and Strauch, Peter}, title = {Tetrahalidocuprates(II) - structure and EPR spectroscopy}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-95012}, pages = {1019 -- 1030}, year = {2013}, abstract = {We present and discuss the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of five tetrachloridocuprate(II) complexes to supply a useful tool for the structural characterisation of the [CuCl4]2- moiety in the liquid state, for example in ionic liquids, or in solution. Bis(benzyltriethylammonium)-, bis(trimethylphenylammonium)-, bis(ethyltriphenylphosphonium)-, bis(benzyltriphenylphosphonium)-, and bis(tetraphenylarsonium)tetrachloridocuprate(II) were synthesised and characterised by elemental, IR, EPR and X-ray analyses. The results of the crystallographic analyses show distorted tetrahedral coordination geometry of all [CuCl4]2- anions in the five complexes and prove that all investigated complexes are stabilised by hydrogen bonds of different intensities. Despite the use of sterically demanding ammonium, phosphonium and arsonium cations to obtain the separation of the paramagnetic Cu(II) centres for EPR spectroscopy no hyperfine structure was observed in the EPR spectra but the principal values of the electron Zeeman tensor, g∥ and g⊥, could be determined. With these EPR data and the crystallographic parameters we were able to carry out a correlation study to anticipate the structural situation of tetrachloridocuprates in different physical states. This correlation is in good agreement with DFT calculations.}, language = {en} }