Composition Space Analysis in the Development of Copper Molybdate Hybrids Decorated by a Bifunctional Pyrazolyl/1,2,4-Triazole Ligand

A bitopic ligand, 4-(3,5-dimethylpyrazol-4-yl)-1,2,4-triazole (Hpz-tr) (1), containing two different heterocyclic moieties was employed for the design of copper(II)–molybdate solids under hydrothermal conditions. In the multicomponent CuII/Hpz-tr/MoVI system, a diverse set of coordination hybrids, [Cu(Hpz-tr)2SO4]·3H2O (2), [Cu(Hpz-tr)Mo3O10] (3), [Cu4(OH)4(Hpz-tr)4Mo8O26]·6H2O (4), [Cu(Hpz-tr)2Mo4O13] (5), and [Mo2O6(Hpz-tr)]·H2O (6), was prepared and characterized. A systematic investigation of these systems in the form of a ternary crystallization diagram approach was utilized to show the influence of the molar ratios of starting reagents, the metal (CuII and MoVI) sources, the temperature, etc., on the reaction products outcome. Complexes 2–4 dominate throughout a wide crystallization range of the composition triangle, while the other two compounds 5 and 6 crystallize as minor phases in a narrow concentration range. In the crystal structures of 2–6, the organic ligand behaves as a short [N–N]-triazole linker between metal centers Cu···Cu in 2–4, Cu···Mo in 5, and Mo···Mo in 6, while the pyrazolyl function remains uncoordinated. This is the reason for the exceptional formation of low-dimensional coordination motifs: 1D for 2, 4, and 6 and 2D for 3 and 5. In all cases, the pyrazolyl group is involved in H bonding (H-donor/H-acceptor) and is responsible for π–π stacking, thus connecting the chain and layer structures in more complicated H-bonding architectures. These compounds possess moderate thermal stability up to 250–300 °C. The magnetic measurements were performed for 2–4, revealing in all three cases antiferromagnetic exchange interactions between neighboring CuII centers and long-range order with a net moment below Tc of 13 K for compound 4.

Vegetation Changes and Timberline Fluctuations in the Central Alps as Indicators of Holocene Climatic Oscillations

Pollen and plant-macrofossil data are presented for two lakes near the timberline in the Italian (Lago Basso, 2250 m) and Swiss Central Alps (Gouille Rion, 2343 m). The reforestation at both sites started at 9700-9500 BP with Pinus cembra, Larbc decidua, and Betula. The timberline reached its highest elevation between 8700 and 5000 BP and retreated after 5000 BP, due to a mid-Holocene climatic change and increasing human impact since about 3500 BP (Bronze Age). The expansion of Picea abies at Lago Basso between ca. 7500 and 6200 BP was probably favored by cold phases accompanied by increased oceanicity, whereas in the area of Gouille Rion, where spruce expanded rather late (between 4500 and 3500 BP), human influence equally might have been important. The mass expansion of Alnus viridis between ca. 5000 and 3500 BP probably can be related to both climatic change and human activity at timberline. During the early and middle Holocene a series of timberline fluctuations is recorded as declines in pollen and macrofossil concentrations of the major tree species, and as increases in nonarboreal pollen in the pollen percentage diagram of Gouille Rion. Most of ·the periods of low timberline can be correlated by radiocarbon dating with climatic changes in the Alps as indicated by glacier ad­ vances in combination with palynological records, solifluction, and dendrocli­ matical data. Lago Basso and Gouille Rion are the only sites in the Alps showing complete palaeobotanical records of cold phases between 10,000 and 2000 BP with very good time control. The altitudinal range of the Holocene treeline fluc­ tuations caused by climate most likely was not more than 100 to 150 m. A possible correlation of a cold period at ca. 7500-6500 BP (Misox oscil­ lation) in the Alps is made with paleoecological data from North America and Scandinavia and a climatic signal in the GRIP ice core from central Greenland 8200 yr ago (ca. 7400 yr uncal. BP).