TY - JOUR A1 - Kammer, Stefan A1 - Starke, Ines A1 - Pietrucha, Andreas A1 - Kelling, Alexandra A1 - Mickler, Wulfhard A1 - Schilde, Uwe A1 - Dosche, Carsten A1 - Kleinpeter, Erich A1 - Holdt, Hans-Jürgen T1 - 1,12-Diazaperylene and 2,11-dialkylated-1,12-diazaperylene iridium(III) complexes [Ir((CN)-N-boolean AND)(2)((NN)-N-boolean AND)]PF6: new supramolecular assemblies JF - Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry N2 - A series of new monocationic iridium(III) complexes [Ir((CN)-N-boolean AND)(2)((NN)-N-boolean AND)]PF6 with "large-surface" alpha,alpha'-diimin ligands (NN)-N-boolean AND (dap = 1,12-diazaperylene, dmedap = 2,11-dimethyl-1,12-diazaperylene, dipdap = 2,11-diisopropyl-1,12-diazaperylene) and different cyclometalating ligands (CN)-N-boolean AND (piq = 1-phenylisoquinoline, bzq = benzo[h]quinoline, ppz = 1-phenylpyrazole, thpy = 2-(2-thienyl)pyridine, ppy = 2-phenylpyridine, meppy = 2-(4-methylphenyl)pyridine, dfppy = 2-(2,4-difluorophenyl)pyridine) were synthesized. The solid structures of the complexes [Ir(piq)(2)(dap)]PF6, [Ir(bzq)(2)(dap)]PF6, [Ir(ppy)(2)(dipdap)]PF6, [Ir(piq)(2)(dmedap)]PF6, [Ir(ppy)(2)(dap)]PF6 and [Ir(ppz)(2)(dap)]PF6 are reported. In [Ir(piq)(2)(dap)]PF6, the dap ligand and one of the piq ligands of each cationic complex are involved in pi-pi stacking interactions forming supramolecular channels running along the crystallographic c axis. In the crystalline [Ir(bzq)(2)(dap)]PF6 pi-pi stacking interactions between the metal complexes lead to the formation of a 2D layer structure. In addition, CH-pi interactions were found in all compounds, which are what stabilizes the solid structure. In particular, a significant number of them were found in [Ir(piq)(2)(dap)]PF6 and [Ir(bzq)(2)(dap)]PF6. The crystal structures of [Ir(ppy)(2)(dipdap)]PF6 and [Ir(ppy)(2)(dmedap)]PF6 are also presented, being the first examples of bis-cyclometalated iridium(III) complexes with phenanthroline-type alpha,alpha'-diimin ligands bearing bulky alkyl groups in the neighbourhood of the N-donor atoms. These ligands implicate a distorted octahedral coordination geometry that in turn destabilized the Ir-N-N boolean AND N bonds. The new iridium (III) complexes are not luminescent. All compounds show an electrochemically irreversible anodic peak between 1.15 and 1.58 V, which is influenced by the different cyclometalated ligands. All of the new complexes show two reversible successive one-electron "large-surface" ligand-centred reductions around -0.70 V and -1.30 V. Electrospray ionisation mass spectrometry (ESI-MS) and collision induced decomposition (CID) measurements were used to investigate the stability of the new complexes. Thereby, the stability agreed well with the order of the Ir-N-N boolean AND N bond lengths. Y1 - 2012 U6 - https://doi.org/10.1039/c2dt30412k SN - 1477-9226 VL - 41 IS - 34 SP - 10219 EP - 10227 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Kammer, Stefan A1 - Kelling, Alexandra A1 - Baier, Heiko A1 - Mickler, Wulfhard A1 - Dosche, Carsten A1 - Rurack, Knut A1 - Kapp, Andreas A1 - Lisdat, Fred A1 - Holdt, Hans-Jürgen T1 - 2,11-dialkylated 1,12-diazaperylene copper(I) complexes : first supramolecular column assemblies by pi-pi stacking between homoleptic tetrahedral metal complexes, exhibiting low-energy MLCT transitions N2 - 2,11-Dialkylated 1,12-diazaperylenes (alkyl = Me, Et, iPr) dmedap, detdap and dipdap have been synthesized by reductive cyclization of 3,3-dialkylated 1,1-biisoquinolines 3a-c, resulting in the first copper(I) complexes of a large- surface ligand. The new copper(I) complexes show low-energy MLCT absorptions unprecedented for bis(-diimin)copper(I) complexes. The solid structures of the complexes[Cu(dipdap)2]BF4·CH2Cl2·1.5H2O, [Cu(dipdap)2]OTf·CH2Cl2, [Cu(dipdap)2]I·C2H4Cl2·THF·2H2O, [Cu(dmedap)2]OTf and [Cu(dipdap)2]AQSO3·H2O (AQSO3 = sodium 9,10-dihydro-9,10-dioxo-2- anthracenesulfonate) are reported. In [Cu(dipdap)2]BF4·CH2Cl2·1.5H2O, each copper(I) complex cation interacts with two others by - stacking interactions forming a novel supramolecular column structural motif running along the crystallographic c axis. In the crystalline compound [Cu(dipdap)2]AQSO3·H2O, aggregation between two complex cations and two additional anions by - stacking interactions is observed, leading to a tetrameric assembly. Furthermore, the three complex compounds [Cu(L)2]BF4 (L = dmedap, detdap, dipdap) were tested for sensory applications in aqueous buffer solutions in electrochemical studies of the complex immobilized on glassy carbon electrodes. Y1 - 2009 UR - http://www3.interscience.wiley.com/journal/27721/home U6 - https://doi.org/10.1002/ejic.200900695 SN - 1434-1948 ER - TY - JOUR A1 - Mickler, Wulfhard T1 - Abtrennung von Schwermetallen aus Deponiesickerwässern durch Reaktivextraktion N2 - Am Beispiel eines modellierten Deponiesickerwassers wird die Möglichkeit einer simultanen Reaktivextraktion von toxischen Schwermetallen aus einer unproblematischen Matrix vorgestellt. Als Extraktionsmittel werden vergleichend Alkylphosphorsäuren (kommerzielle D2EHPA, D2EHTPA), ß-Diketone, 4-Acylpyrazol-5-one und eine neuartige kommerzielle Alkylphosphonsäure eingesetzt. Die thermodynamischen Parameter der Extraktion lassen sich mit Hilfe der Funktionen %E = f( t, pH), lg D = f ( pH, cL) bestimmen. Einflüsse von Lösungsmitteln und konkurrierende Komplexbildner in der wäßrigen Phase auf das Verteilungsgleichgewicht werden diskutiert. Inhaltsstoffe der wäßrigen Phase (Cyanid, Tartrat, Ammoniak, Huminsäuren oder Chlorid) beeinflussen entsprechend ihrer Ligandstärke die Metallabtrennung. Für den Fall der Huminsäure wird eine Größenordnung von Weinsäure gefunden. Sulfationen erschweren zusätzlich die Extraktion von Calcium. Halogenierte und aromatische Verdünnungsmittel haben gegenüber unproblematischen Kohlenwasserstoffen keinen Vorteil. Mit Aminomethylphosphonsäure (Ironex, BASF) gelingt eine quantitative Eisen, Indium- und Galliumabtrennung bei einem pH-Wert kleiner 1.5 als ML2(HL) bzw. ML(HL)2. Kupfer und Zink werden im pH-Bereich von 4-6 quantitativ als 1:2- Komplex extrahiert. Insgesamt günstige Ergebnisse zeigen die ß-Diketone (auch LIX 54) und 4-Acylpyrazol-5-one. Hier ergibt sich die Möglichkeit toxische Schwermetalle selektiv abzutrennen und eine unproblematische Matrix zu gewinnen, da Calcium nur zu 6% und Magnesium zu 23% extrahiert werden. Y1 - 2000 ER - TY - JOUR A1 - Mickler, Wulfhard T1 - Abtrennung von Schwermetallen aus Deponiesickerwässern durch Reaktivextraktion Y1 - 1999 SN - 3- 9805032-7-5 ER - TY - JOUR A1 - Uhlemann, Erhard A1 - Labuda, Jan A1 - Vanickova, M. A1 - Mickler, Wulfhard T1 - Applicability of chemically modified electrodes for the determination of copper species in natural water Y1 - 1994 ER - TY - JOUR A1 - Träger, Juliane A1 - Klamroth, Tillmann A1 - Kelling, Alexandra A1 - Lubahn, Susanne A1 - Cleve, Ernst A1 - Mickler, Wulfhard A1 - Heydenreich, Matthias A1 - Müller, Holger A1 - Holdt, Hans-Jürgen T1 - Complexation of Palladium(II) with unsaturated Dithioethers a systematic development of highly selective ligands for solvent extraction JF - European journal of inorganic chemistry : a journal of ChemPubSoc Europe N2 - There is a demand for new and robust PdII extractants due to growing recycling rates. Chelating dithioethers are promising substances for solvent extraction as they form stable square-planar complexes with PdII. We have modified unsaturated dithioethers, which are known to coordinate PdII, and adapted them to the requirements of industrial practice. The ligands are analogues of 1,2-dithioethene with varying electron-withdrawing backbones and polar end-groups. The crystal structures of several ligands and their palladium complexes were determined as well as their electro- and photochemical properties, complex stability and behaviour in solution. Solvent extraction experiments showed the superiority of some of our ligands over conventionally used extractants in terms of their very fast reaction rates. With highly selective 1,2-bis(2-methoxyethylthio)benzene (4) it is possible to extract PdII from a highly acidic medium in the presence of other base and palladium-group metals. KW - Renewable resources KW - Palladium KW - Chelates KW - Ligand design KW - S li-gands Y1 - 2012 U6 - https://doi.org/10.1002/ejic.201101406 SN - 1434-1948 IS - 14 SP - 2341 EP - 2352 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Schilde, Uwe A1 - Mickler, Wulfhard A1 - Uhlemann, Erhard T1 - Crystal structure of bis(1-phenyl-5-cyclohexyl-pentane-1,3-dionato-copper(II) Y1 - 1997 SN - 0044-2968 ER - TY - JOUR A1 - Uhlemann, Erhard A1 - Schilde, Uwe A1 - Mickler, Wulfhard T1 - Crystal structure of bis(1-phenyldecane-1,3-dionato)-copper(II), Cu(C16H21O2)2 Y1 - 1996 SN - 0044-2968 ER - TY - JOUR A1 - Janiak, Chr. A1 - Scharmann, T. G. A1 - Green, J. C. A1 - Parkin, R. P. G. A1 - Kolm, M. J. A1 - Riedel, E. A1 - Mickler, Wulfhard A1 - Elguero, J. A1 - Claramunt, R. M. A1 - Sanz, D. T1 - Effects of nitrogen substitution in Poly(pyrazolyl)borato Ligands : from orbital energy levels to C-H...O Hydrogen Bonding Y1 - 1996 ER - TY - JOUR A1 - Mickler, Wulfhard A1 - Mönner, Anke A1 - Uhlemann, Erhard T1 - Electrochemical studies on the stability of copper ß-diketone chelates Y1 - 1998 ER - TY - JOUR A1 - Awad, Duha Jawad A1 - Koch, Andreas A1 - Mickler, Wulfhard A1 - Schilde, Uwe A1 - Strauch, Peter T1 - EPR spectroscopy of 4, 4 '-Bis(tert-butyl)-2, 2 '-bipyridine-1, 2-dithiolatocuprates(II) in host lattices with different coordination geometries JF - Zeitschrift für anorganische und allgemeine Chemie N2 - 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. KW - 1 KW - 2-Dithiosquarate KW - 1 KW - 2-Dithiooxalate KW - 1 KW - 2-Dicyanoethene-1 KW - 2-dithiolate KW - 4 KW - 4'-Bis(tert-butyl)-2 KW - 2'-bipyridine KW - X-ray structure KW - EPR KW - Copper KW - Nickel KW - Zinc Y1 - 2012 U6 - https://doi.org/10.1002/zaac.201100517 SN - 0044-2313 VL - 638 IS - 6 SP - 965 EP - 975 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Mickler, Wulfhard A1 - Reich, Annett A1 - Uhlemann, Erhard T1 - Extraction of iron (II) and iron (III) with 4-acylpyrazolones in comparision with long chain 1-phenyl-1,3- (cyclo)alkanediones Y1 - 1998 ER - TY - JOUR A1 - Uhlemann, Erhard A1 - Mickler, Wulfhard A1 - Reich, Annett T1 - Extraction of zinc with long-chain ß-Diketones and 4-Acyl-5-Pyrazolones Y1 - 1995 ER - TY - JOUR A1 - Brietzke, Thomas Martin A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Mickler, Wulfhard A1 - Holdt, Hans-Jürgen T1 - Heterodinuclear Ruthenium(II) Complexes of the Bridging Ligand 1,6,7,12-Tetraazaperylene with Iron(II), Cobalt(II), Nickel(II), as well as Palladium(II) and Platinum(II) JF - Zeitschrift für anorganische und allgemeine Chemie N2 - The first heterodinuclear ruthenium(II) complexes of the 1,6,7,12-tetraazaperylene (tape) bridging ligand with iron(II), cobalt(II), and nickel(II) were synthesized and characterized. The metal coordination sphere in this complexes is filled by the tetradentate N,N-dimethyl-2,11-diaza[3.3](2,6)-pyridinophane (L-N4Me2) ligand, yielding complexes of the general formula [(L-N4Me2)Ru(mu-tape)M(L-N4Me2)](ClO4)(2)(PF6)(2) with M = Fe {[2](ClO4)(2)(PF6)(2)}, Co {[3](ClO4)(2)(PF6)(2)}, and Ni {[4](ClO4)(2)(PF6)(2)}. Furthermore, the heterodinuclear tape ruthenium(II) complexes with palladium(II)- and platinum(II)-dichloride [(bpy)(2)Ru(-tape)PdCl2](PF6)(2) {[5](PF6)(2)} and [(dmbpy)(2)Ru(-tape)PtCl2](PF6)(2) {[6](PF6)(2)}, respectively were also prepared. The molecular structures of the complex cations [2](4+) and [4](4+) were discussed on the basis of the X-ray structures of [2](ClO4)(4)MeCN and [4](ClO4)(4)MeCN. The electrochemical behavior and the UV/Vis absorption spectra of the heterodinuclear tape ruthenium(II) complexes were explored and compared with the data of the analogous mono- and homodinuclear ruthenium(II) complexes of the tape bridging ligand. KW - N ligands KW - Ruthenium KW - Structure elucidation KW - Charge transfer KW - Electrochemistry Y1 - 2016 U6 - https://doi.org/10.1002/zaac.201500645 SN - 0044-2313 SN - 1521-3749 VL - 642 SP - 8 EP - 13 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Ast, Sandra A1 - Fischer, Tobias A1 - Müller, Holger A1 - Mickler, Wulfhard A1 - Schwichtenberg, Mathias A1 - Rurack, Knut A1 - Holdt, Hans-Jürgen T1 - Integration of the 1,2,3-Triazole "Click" Motif as a potent signalling element in metal ion responsive fluorescent probes JF - Chemistry - a European journal N2 - In a systematic approach we synthesized a new series of fluorescent probes incorporating donoracceptor (D-A) substituted 1,2,3-triazoles as conjugative -linkers between the alkali metal ion receptor N-phenylaza-[18]crown-6 and different fluorophoric groups with different electron-acceptor properties (4-naphthalimide, meso-phenyl-BODIPY and 9-anthracene) and investigated their performance in organic and aqueous environments (physiological conditions). In the charge-transfer (CT) type probes 1, 2 and 7, the fluorescence is almost completely quenched by intramolecular CT (ICT) processes involving charge-separated states. In the presence of Na+ and K+ ICT is interrupted, which resulted in a lighting-up of the fluorescence in acetonitrile. Among the investigated fluoroionophores, compound 7, which contains a 9-anthracenyl moiety as the electron-accepting fluorophore, is the only probe which retains light-up features in water and works as a highly K+/Na+-selective probe under simulated physiological conditions. Virtually decoupled BODIPY-based 6 and photoinduced electron transfer (PET) type probes 35, where the 10-substituted anthracen-9-yl fluorophores are connected to the 1,2,3-triazole through a methylene spacer, show strong ion-induced fluorescence enhancement in acetonitrile, but not under physiological conditions. Electrochemical studies and theoretical calculations were used to assess and support the underlying mechanisms for the new ICT and PET 1,2,3-triazole fluoroionophores. KW - charge transfer KW - click chemistry KW - electron transfer KW - fluorescent probes KW - metal ions Y1 - 2013 U6 - https://doi.org/10.1002/chem.201201575 SN - 0947-6539 VL - 19 IS - 9 SP - 2990 EP - 3005 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Uhlemann, Erhard A1 - Prochaska, Krystyna A1 - Lozynski, M. A1 - Szymanowski, Jan A1 - Mickler, Wulfhard T1 - Interfacial activity and semiempirical PM3 calculations of 2-Ethylhexanoylbenzoyl Methane Y1 - 1996 ER - TY - JOUR A1 - Uhlemann, Erhard A1 - Friedrich, Alwin A1 - Hinsche, Gerald A1 - Mickler, Wulfhard A1 - Schilde, Uwe T1 - Komplexbildung und Metallextraktion mit heterocyclischen ß-Dicarbonylverbindungen im Vergleich : Struktur von 3-Phenyl-4-benzoyl-isoxazol-5-on Y1 - 1995 ER - TY - JOUR A1 - Uhlemann, Erhard A1 - Mickler, Wulfhard A1 - Reich, Annett A1 - Bart, Hans-Joerg T1 - Liquid membrane permeation of zinc, cadmium and nickel with 4-acyl-5-pyrazolones and ß-diketones Y1 - 1996 ER - TY - JOUR A1 - Mickler, Wulfhard T1 - Liquid-liquid-extraction of copper from ammoniacal solution with 4-acylpyrazol-5-ones and ß-diketones Y1 - 1993 SN - 1-85861-042-7 ER - TY - JOUR A1 - Mickler, Wulfhard A1 - Uhlemann, Erhard T1 - Liquid-Liquid-Extraction of copper from ammoniacal solution with cyclohexyl substituted ß-diketones Y1 - 1993 ER -