A Soluble Equivalent of the Supramolecular, Quasi-One-Dimensional, Semiconducting Magnus' Green Salt
文摘
A soluble supramolecular, quasi-one-dimensional semiconducting complex comprisingalternately stacked [Pt(NH2dmoc)4]2+ and [PtCl4]2- units, where dmoc denotes (S)-3,7-dimethyloctyl, has been synthesized and characterized with various methods. In contrast toearlier enunciated expectations and unlike nearly all other known derivatives, [Pt(NH2dmoc)4][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(NH2dmoc)4][PtCl4] was established to be 3.1 Å from powder X-ray andelectron diffraction patterns. Similar to Magnus' green salt, [Pt(NH2dmoc)4][PtCl4] was foundto be a semiconductor with a thermal activation energy of 0.24 eV and an electricalconductivity of 1.6 × 10-7 S/cm at room temperature. Although Magnus' green salt virtuallyis intractable, [Pt(NH2dmoc)4][PtCl4] was soluble in common organic solvents. Remarkably,strong evidence indicated that self-assembled platinum chain structures were present alsoin solution. Hence, [Pt(NH2dmoc)4][PtCl4] may indeed be regarded as a processible form ofMagnus' green salt.