4.8 Article

A soluble equivalent of the supramolecular, quasi-one-dimensional, semiconducting Magnus' green salt

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CHEMISTRY OF MATERIALS
卷 14, 期 4, 页码 1730-1735

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AMER CHEMICAL SOC
DOI: 10.1021/cm0109793

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A soluble supramolecular, quasi-one-dimensional semiconducting complex comprising alternately stacked [Pt(NH(2)dmoc)(4)](2+) and [PtCl4](2-) units, where dmoc denotes (S)-3,7-dimethyloctyl, has been synthesized and characterized with various methods. In contrast to earlier enunciated expectations and unlike nearly all other known derivatives, [Pt(NH2dmoc)41 [PtCl4] showed the color of Magnus' green salt, [Pt(NH3)(4)] [PtCl4], which is characteristic for linearly arranged platinum atoms with considerable Pt-Pt interactions. The Pt-Pt distance in [Pt(NH(2)dmoc)(4)] [PtCl4] was established to be 3.1 Angstrom from powder X-ray and electron diffraction patterns. Similar to Magnus' green salt, [Pt(NH(2)dmoc)(4)] [PtCl4] was found to be a semiconductor with a thermal activation energy of 0.24 eV and an electrical conductivity of 1.6 x 10(-7) S/cm at room temperature, Although Magnus' green salt virtually is intractable, [Pt(NH(2)dmoc)(4)] [PtCl4] was soluble in common organic solvents. Remarkably, strong evidence indicated that self-assembled platinum chain structures were present also in solution. Hence, [Pt(NH(2)dmoc)(4)][PtCl4] may indeed be regarded as a processible form of Magnus' green salt.

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