Synthesis, processing, and characterization are reported for a series of tetracyanoplatinate Magnus’ salt (TCN-MS) derivatives—soluble derivatives of the generally intractable Magnus’ green salt—that feature the general structure [Pt(NH₂R)₄][Pt(CN)₄] where R is a branched alkyl group or a ω-phenylalkyl group. In solutions, these coordination compounds generally dissolve on the level of individual ion pairs as shown by X-ray diffraction analysis. To enable the formation of quasi-one-dimensional linear stacks of Pt(II) atoms in thin films, the matrix-assisted assembly is employed, whereby the compounds are codissolved with poly(ethylene oxide) (PEO), followed by film casting, thermally activated assembly, and eventual removal of PEO. Remarkably, assembled TCN-MS inorganic polymers exhibit bright blue-green photoluminescence. A detailed investigation of the assembly process and simultaneously modified solid-state optical properties is performed using a range of microscopy, optical and vibrational spectroscopy, and thermal analysis techniques. Given their unusual combination of optical properties, namely, transparency in the visible region, high photoluminescence quantum efficiencies (up to 13% in first-demonstration samples), and large Stokes shifts (up to 1 eV), TCN-MS derivatives are proposed as a promising class of light-emitting materials for emerging applications in molecular optoelectronics, the potential and challenges of which are discussed.

Assembly-Induced Bright-Light Emission from Solution-Processed Platinum(II) Inorganic Polymers