Modellkomplexe zur Sauerstoffaktivierung auf Basis des 1,3,4-Thiadiazols

Das Ziel der vorliegenden Arbeit waren die Synthese und Untersuchung von Modellverbindungen zur Sauerstoffaktivierung auf der Basis neuer Ligandensysteme des 1,3,4-Thiadiazols unter Ausarbeitung einer Synthesestrategie zur Derivatisierung der heteroaromatischen 1,3,4-Thiadiazol-Liganden, deren Koordinationsverhalten in Abhängigkeit ihres 2,5-Substitutionsmusters untersucht wurde, sowie die fortführende Bearbeitung bereits bekannter Ligandensysteme zur Erzeugung von homo- und heterovalenten Übergangsmetallkomplexverbindungen.rnDie unter der Verwendung der modifizierten Liganden TPDE, H1TPDP und H1BPMP resultierenden dinuklearen Komplexverbindungen zeigen unterschiedlich starke antiferromagnetische Wechselwirkungen in Abhängigkeit der vorhandenen Brückenliganden. In der Verbindung [Fe6O2(OH)(L´)2(OOCMe3)9(OEt)2] trat eine Fragmentierung des Liganden H1TPDP auf. Das cisoide Ligandensubstitutionsmuster der entstandenen sechskernigen Verbindung ist verantwortlich für die interessanten magnetischen Eigenschaften des Komplexes. rnNeue Perspektiven zur Erzeugung von Modellverbindungen zur Sauerstoffaktivierung wurden mit dem Mono-Chelatliganden H1ETHP und den Bis-Chelatliganden HL2H, H2L2H und H2BATP aufgezeigt. Die Umsetzung von H1ETHP mit verschiedenen Übergangsmetallsalzen resultierte für die Metalle Cr(III), Fe(III), Co(III) und Ni(II) in mononuklearen Verbindungen des Typs [M(ETHP)2]X (X = ClO4, FeCl4, OMe, Cl, Br) sowie in zwei tetranuklearen Verbindungen mit Mn(II) und Cu(II). [Mn4(ETHP)6] besitzt ein propellerförmiges, planares [Mn4O6]2+-System mit einen Spingrundzustand von S = 5. In allen Verbindungen von H1ETHP konnte eine mono-κN-Koordination des 1,3,4-Thiadiazol-Rückgrates über eines seiner beiden endozyklischen Stickstoffdonoratome beobachtet werden. rnAus Umsetzungen der Bis-Chelatliganden wurden fast ausschließlich polynukleare Übergangsmetallkomplexe erhalten. Insbesondere der Ligand H2L2H zeigt eine ausgeprägte Tendenz zur Ausbildung trinuklearer, linearer Komplexe, welche auf Grund ihrer ungeraden Anzahl von Übergangsmetallionen einen Spingrundzustand S ≠ 0 aufweisen.rn Die mit dem Liganden HL2H erhaltenen Verbindungen unterstreichen die hohe Flexibilität dieser Systeme hinsichtlich der Erzeugung polynuklearer und heterovalenter Komplexverbindungen. So konnten in Abhängigkeit vom verwendeten Übergangsmetallsalz trinukleare, pentanukleare, aber auch hepta- und oktanukleare Verbindungen synthetisiert werden. Insbesondere die Komplexe des Mangans und des Cobalts zeigen ein heterovalentes [MnIIMnIII4]- bzw. [CoII2CoIII3]-Motiv, was sich in Spingrundzuständen von S ≠ 0 äußert. Der diamagnetische, achtkernige Fe8-Cluster besitzt eine pseudo C3-symmetrische Anordnung der Metall-Zentren, während für die heptanukleare Cu7-Kette durch ihre stark unterschiedlichen Kupfer-Koordinationsgeometrien interessante magnetische Austauschwechselwirkungen beobachtet werden konnten. Der dreikernige µ3-oxo-verbrückte Komplex des Liganden H2BATP zeigt als interessante strukturelle Eigenschaft ein ein µ3-Verbrückungsmuster des eingesetzten Sulfat-Anions. rnIn allen Komplexen der Bis-Chelatliganden HL2H, H2L2H und H2BATP konnte ein µ2-κN,κN-Koordiantionsmodus des 1,3,4-Thiadiazols und somit eine Abhängigkeit der Verbrückung vom Ligandensubstitutionsmuster beobachtet werden.rn

A 700-year paleoecological record of boreal ecosystem responses to climatic variation from Alaska

Recent observations and model simulations have highlighted the sensitivity of the forest - tundra ecotone to climatic forcing. In contrast, paleoecological studies have not provided evidence of tree-line fluctuations in response to Holocene climatic changes in Alaska, suggesting that the forest - tundra boundary in certain areas may be relatively stable at multicentennial to millennial time scales. We conducted a multiproxy study of sediment cores from an Alaskan lake near the altitudinal limits of key boreal-forest species. Paleoecological data were compared with independent climatic reconstructions to assess ecosystem responses of the forest - tundra boundary to Little Ice Age (LIA) climatic. uctuations. Pollen, diatom, charcoal, macrofossil, and magnetic analyses provide the first continuous record of vegetation -. re - climate interactions at decadal to centennial time scales during the past 700 years from southern Alaska. Boreal-forest diebacks characterized by declines of Picea mariana, P. glauca, and tree Betula occurred during the LIA ( AD 1500 - 1800), whereas shrubs ( Alnus viridis, Betula glandulosa/nana) and herbaceous taxa (Epilobium, Aconitum) expanded. Marked increases in charcoal abundance and changes in magnetic properties suggest increases in. re importance and soil erosion during the same period. In addition, the conspicuous reduction or disappearance of certain aquatic ( e. g., Isoetes, Nuphar, Pediastrum) and wetland ( Sphagnum) plants and major shifts in diatom assemblages suggest pronounced lake-level. uctuations and rapid ecosystem reorganization in response to LIA climatic deterioration. Our results imply that temperature shifts of 1 - 2 degrees C, when accompanied by major changes in moisture balance, can greatly alter high-altitudinal terrestrial, wetland, and aquatic ecosystems, including conversion between boreal-forest tree line and tundra. The climatic and ecosystem variations in our study area appear to be coherent with changes in solar irradiance, suggesting that changes in solar activity contributed to the environmental instability of the past 700 years.

Metamagnetic Copper(II) Diphosphonates with Layered Structures

Compounds [NH3(CH2)4NH3]Cu3(hedp)2·2H2O (1) and [NH3(CH2)3NH3]Cu3(hedp)2·3.5H2O (2), where hedp represents 1-hydroxyethylidenediphosphonate, exhibit two-dimensional structures closely related to each other. The anionic layers with composition {Cu3(hedp)2}n2n- contain four- and eight-membered rings assembled from vertex-sharing {CuO4} units and {CPO3} tetrahedra. The protonated diamines and lattice water fill the interlayer spaces. Crystal data for 2:  space group P1̄, a = 8.0315(4), b = 11.3713(6), c = 13.3117(7) Å, α = 97.122(1), β = 103.187(1), γ = 108.668(1)°, V = 1095.5(1) Å3, Z = 2. Magnetic properties of the two compounds have been investigated. Both show typical metamagnetic behaviors at low temperature. The critical field at which the antiferromagnetic ground-state switches to a ferrimagnetic state is ∼48 Oe for 1 and 185 Oe for 2 at about 2 K.

The Exploitation of Versatile Building Blocks for the Self-Assembly of Novel Molecular Magnets

Using molecular building blocks to self-assemble lattices supporting long-range magnetic order is currently an active area of solid-state chemistry. Consequently, it is the realm of supramolecular chemistry that synthetic chemists are turning to in order to develop techniques for the synthesis of structurally well-defined supramolecular materials. In recent years we have investigated the versatility and usefulness of two classes of molecular building blocks, namely, tris-oxalato transition-metal (M. Pilkington and S. Decurtins, in “Magnetoscience—From Molecules to Materials,” Wiley–VCH, 2000), and octacyanometalate complexes (Pilkington and Decurtins, Chimia 54, 593 (2001)), for applications in the field of molecule-based magnets. Anionic, tris-chelated oxalato building blocks are able to build up two-dimensional honeycomb-layered structural motifs as well as three-dimensional decagon frameworks. The discrimination between the crystallization of the two- or three-dimensional structures relies on the choice of the templating counterions (Decurtins, Chimia 52, 539 (1998); Decurtins et al. Mol. Cryst. Liq. Cryst. 273, 167 (1995); New J. Chem. 117 (1998)). These structural types display a range of ferro, ferri, and antiferromagnetic properties (Pilkington and Decurtins, in “Magnetoscience—From Molecules to Materials”). Octacyanometalate building blocks self-assemble to afford two new classes of cyano-bridged compounds namely, molecular clusters and extended three dimensional networks (J. Larionova et al., Angew. Chem. Int. Ed. 39, 1605 (2000); Pilkington et al., in preparation). The molecular cluster with a MnII9MoV6 core has the highest ground state spin value, S=51/2, reported to-date (Larionova et al., Angew. Chem. Int. Ed. 39, 1605 (2000)). In the high-temperature regime, the magnetic properties are characterized by ferromagnetic intracluster coupling. In the magnetic range below 44 K, the magnetic cluster signature is lost as possibly a bulk behavior starts to emerge. The three-dimensional networks exhibit both paramagnetic and ferromagnetic behavior, since the magnetic properties of these materials directly reflect the electronic configuration of the metal ion incorporated into the octacyanometalate building blocks (Pilkington et al., in preparation). For both the oxalate- and cyanide-bridged materials, we are able to manipulate the magnetic properties of the supramolecular assemblies by tuning the electronic configurations of the metal ions incorporated into the appropriate molecular building blocks (Pilkington and Decurtins, in “Magnetoscience—From Molecules to Materials,” Chimia 54, 593 (2000)).

A new 1D bimetallic thiocyanate-bridged copper(II)–cobalt(II) compound

The crystal structure of the first one-dimensional hetero-metallic compound containing thiocyanate as bridging ligands,{[Cu(cyclam)][Co(NCS)4]}n, has been determined, togetherwith a preliminary study of the magnetic properties.

Sediments of Lake Vens (SW European Alps, France) record large-magnitude earthquake events

We studied sediment cores from Lake Vens (2,327 m asl), in the Tinée Valley of the SW Alps, to test the paleoseismic archive potential of the lake sediments in this particularly earthquake-sensitive area. The historical earthquake catalogue shows that moderate to strong earthquakes, with intensities of IX–X, have impacted the Southern Alps during the last millennium. Sedimentological (X-ray images, grain size distribution) and geochemical (major elements and organic matter) analyses show that Lake Vens sediments consist of a terrigenous, silty material (minerals and organic matter) sourced from the watershed and diatom frustules. A combination of X-ray images, grain-size distribution, major elements and magnetic properties shows the presence of six homogenite-type deposits interbedded in the sedimentary background. These sedimentological features are ascribed to sediment reworking and grain sorting caused by earthquake-generated seiches. The presence of microfaults that cross-cut the sediment supports the hypothesis of seismic deposits in this system. A preliminary sediment chronology is provided by 210Pb measurement and AMS 14C ages. According to the chronology, the most recent homogenite events are attributable to damaging historic earthquakes in AD 1887 (Ligure) and 1564 (Roquebillière). Hence, the Lake Vens sediment recorded large-magnitude earthquakes in the region and permits a preliminary estimate of recurrence time for such events of ~400 years.

Late-Holocene climate variability and ecosystem responses in Alaska inferred from high-resolution multiproxy sediment analyses at Grizzly Lake

The late-Holocene shift from Picea glauca (white spruce) to Picea mariana (black spruce) forests marked the establishment of modern boreal forests in Alaska. To understand the patterns and drivers of this vegetational change and the associated late-Holocene environmental dynamics, we analyzed radiocarbon-dated sediments from Grizzly Lake for chironomids, diatoms, pollen, macrofossils, charcoal, element composition, particle size, and magnetic properties for the period 4100–1800 cal BP. Chironomid assemblages reveal two episodes of decreased July temperature, at ca. 3300–3150 (ca −1 °C) and 2900–2550 cal BP (ca −2 °C). These episodes coincided with climate change elsewhere in the Northern Hemisphere, atmospheric reorganization, and low solar activity. Diatom-inferred lake levels dropped by ca. 5 m at 3200 cal BP, suggesting dry conditions during the period 3200–1800 cal BP. P. glauca declined and P. mariana expanded at ca. 3200 cal BP; this vegetational change was linked to diatom-inferred low lake levels and thus decreased moisture availability. Forest cover declined at 3300–3100, 2800–2500 and 2300–2100 cal BP and soil erosion as inferred from increased values of Al, K, Si, Ti, and Ca intensified, when solar irradiance was low. Plant taxa adapted to disturbance and cold climate (e.g. Alnus viridis, shrub Betula, Epilobium) expanded during these periods of reduced forest cover. This open vegetation type was associated with high fire activity that peaked at 2800 cal BP, when climatic conditions were particularly cold and dry. Forest recovery lagged behind subsequent climate warming (≤+3 °C) by ca. 75–225 years. Our multiproxy data set suggests that P. glauca was dominant under warm-moist climatic conditions, whereas P. mariana prevailed under cold-dry and warm-dry conditions. This pattern implies that climatic warming, as anticipated for this century, may promote P. glauca expansions, if moisture availability will be sufficiently high, while P. mariana may expand under dry conditions, possibly exacerbating climate impacts on the fire regime.

Molecular-Based Magnetism in Bimetallic Two-Dimensional Oxalate-Bridged Networks. An X-ray and Neutron Diffraction Study

Bimetallic, oxalate-bridged compounds with bi- and trivalent transition metals comprise a class of layered materials which express a large variety in their molecular-based magnetic behavior. Because of this, the availability of the corresponding single-crystal structural data is essential to the successful interpretation of the experimental magnetic results. We report in this paper the crystal structure and magnetic properties of the ferromagnetic compound {[N(n-C3H7)4][MnIICrIII(C2O4)3]}n (1), the crystal structure of the antiferromagnetic compound {[N(n-C4H9)4][MnIIFeIII(C2O4)3]}n (2), and the results of a neutron diffraction study of a polycrystalline sample of the ferromagnetic compound {[P(C6D5)4][MnIICrIII(C2O4)3]}n (3). Crystal data:  1, rhombohedral, R3c, a = 9.363(3) Å, c = 49.207(27) Å, Z = 6; 2, hexagonal, P63, a = 9.482(2) Å, c = 17.827(8) Å, Z = 2. The structures consist of anionic, two-dimensional, honeycomb networks formed by the oxalate-bridged metal ions, interleaved by the templating cations. Single-crystal field dependent magnetization measurements as well as elastic neutron scattering experiments on the manganese(II)−chromium(III) samples show the existence of long-range ferromagnetic ordering behavior below Tc = 6 K. The magnetic structure corresponds to an alignment of the spins perpendicular to the network layers. In contrast, the manganese(II)−iron(III) compound expresses a two-dimensional antiferromagnetic ordering.

Experimental and Theoretical Electron Density Analysis of Copper Pyrazine Nitrate Quasi-Low-Dimensional Quantum Magnets

The accurate electron density distribution and magnetic properties of two metal-organic polymeric magnets, the quasi-one-dimensional (1D) Cu(pyz)(NO3)2 and the quasi-two-dimensional (2D) [Cu(pyz)2(NO3)]NO3·H2O, have been investigated by high-resolution single-crystal X-ray diffraction and density functional theory calculations on the whole periodic systems and on selected fragments. Topological analyses, based on quantum theory of atoms in molecules, enabled the characterization of possible magnetic exchange pathways and the establishment of relationships between the electron (charge and spin) densities and the exchange-coupling constants. In both compounds, the experimentally observed antiferromagnetic coupling can be quantitatively explained by the Cu-Cu superexchange pathway mediated by the pyrazine bridging ligands, via a σ-type interaction. From topological analyses of experimental charge-density data, we show for the first time that the pyrazine tilt angle does not play a role in determining the strength of the magnetic interaction. Taken in combination with molecular orbital analysis and spin density calculations, we find a synergistic relationship between spin delocalization and spin polarization mechanisms and that both determine the bulk magnetic behavior of these Cu(II)-pyz coordination polymers.