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Merck

Electronically-coupled MM quadruply-bonded complexes of molybdenum and tungsten.

Chemical record (New York, N.Y.) (2005-10-08)
Malcolm H Chisholm, Nathan J Patmore
要旨

The reaction of M2(O2CBu(t))4 (M = Mo, W) with a dicarboxylic acid in toluene yields compounds of general formula [M2]-O2C-X-CO2-[M2] ([M2] = M2(O2CBu(t))3; X = conjugated spacer). The M2 units are electronically coupled via interactions between the M2 delta and dicarboxylate pi* orbitals, and the magnitude of this coupling is revealed by electronic structure calculations and spectroscopic data. These compounds show intense metal to ligand charge transfer (MLCT) absorptions in the visible region of the electronic spectrum that are temperature and solvent dependent. Evidence of electronic coupling is seen in their cyclic voltammograms, which show two successive one-electron oxidations. The extent of electronic coupling in the mixed valence radical cations [M2]-O2C-X-CO2-[M2]+, generated by oxidation with one equivalent of AgPF6 or FeCp2PF6, is evaluated by EPR and UV-vis-NIR spectroscopic data, and delocalized behavior is observed in compounds with W2 units separated by up to 13.6 angstroms. The simplicity of the frontier M2 orbital interactions with the bridge pi orbitals provides a convenient system with which to study electron transfer in mixed valence systems, as compared to the extensively studied, but more complicated, dinuclear t(2g)6/t(2g)5 mixed valence compounds. Oligomeric and polymeric compounds incorporating M2 units have also been synthesized, having general formula [M2(O2CR)2(O2C-Thio-CO2)]n (Thio = n-hexyl substituted ter- and quinque-thiophenes). They can be deposited as thin films by spin coating, and show photoluminescence and electroluminescence. These metallo-polythiophenes show potential for application in electronic materials. (

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製品内容

Sigma-Aldrich
タングステン, powder, 12 μm, 99.9% trace metals basis
Sigma-Aldrich
タングステン, powder, ≤10 μm, ≥99.99% trace metals basis
Sigma-Aldrich
タングステン, powder (monocrystalline), 0.6-1 μm, ≥99.9% trace metals basis
Sigma-Aldrich
タングステン, wire, diam. 0.25 mm, ≥99.9% trace metals basis
Sigma-Aldrich
タングステン, wire, diam. 0.5 mm, ≥99.9% trace metals basis
Sigma-Aldrich
タングステン, wire, diam. 1.0 mm, 99.99% trace metals basis
Sigma-Aldrich
タングステン, foil, thickness 0.25 mm, ≥99.9% trace metals basis
Sigma-Aldrich
タングステン, foil, thickness 0.5 mm, ≥99.9% trace metals basis
タングステン, mesh, 100x100mm, nominal aperture 0.2mm, wire diameter 0.05mm, 100 wires/inch, open area 64%, plain weave mesh, 99.95%
Sigma-Aldrich
タングステン, foil, thickness 0.127 mm, ≥99.9% trace metals basis
タングステン, lump, 100g, max. size 5mm
タングステン, foil, 100x100mm, thickness 0.125mm, as rolled, 99.95%
タングステン, mesh, 50x50mm, nominal aperture 0.2mm, wire diameter 0.05mm, 100 wires/inch, open area 64%, plain weave mesh, 99.95%
タングステン, foil, 200x200mm, thickness 0.3mm, as rolled, 99.95%
タングステン, wire, straight, 500mm, diameter 0.5mm, 99.9+%
タングステン, rod, 100mm, diameter 6.35mm, centerless ground, 99.95%
タングステン, lump, 200g, max. size 5mm
タングステン, mesh, 50x50mm, nominal aperture 0.15mm, wire diameter 0.02mm, 150 wires/inch, open area 75%, plain weave mesh, 99.95%
タングステン, insulated wire, 10m, conductor diameter 0.025mm, insulation thickness 0.005mm, polyimide insulation, 99.9%
タングステン, wire reel, 10m, diameter 0.02mm, gold plated, 99.95%
タングステン, wire reel, 5m, diameter 0.1mm, gold plated, 99.95%
タングステン, rod, 100mm, diameter 3.0mm, centerless ground, 99.95%
タングステン, foil, not light tested, 25x25mm, thickness 0.003mm, 99.95%
タングステン, wire, straight, 300mm, diameter 0.38mm, 99.9+%
タングステン, wire reel, 25m, diameter 0.05mm, clean, 99.95%
タングステン, microfoil, disks, 25mm, thinness 0.25μm, specific density 474μg/cm2, permanent mylar 3.5μm support, 99.95%
タングステン, wire, straight, 100mm, diameter 0.15mm, 99.9+%
タングステン, rod, 200mm, diameter 10.0mm, centerless ground, 99.95%
タングステン, foil, 50x50mm, thickness 0.5mm, as rolled, 99.95%
タングステン, foil, 50x50mm, thickness 0.15mm, as rolled, 99.95%