Semiconducting Manganese-Bipyridyl Coordination Polymer via a Manganese–Metal-Nanoparticle Approach

The coordination polymer [Na2Mn2(4,4′-bipy)7(2,2′-bipy)4] is prepared by a novel redox approach using Mn(0) nanoparticles (2.4 ± 0.3 nm in size) as the starting material. The Mn(0) nanoparticles are then reacted with 2,2′-bipyridine (2,2′-bipy) and 4,4′-bipyridine (4,4′-bipy) in toluene at 80 °C. The title compound is composed of ∞1[Mn(2,2′-bipy)(4,4′-bipy)3/2] chains and double-stranded ∞1[Na2(2,2′-bipy)2(4,4′-bipy)4] chains forming an interpenetrating coordination network with five noncharged bipy ligands and six anionic [bipy]− ligands. Such composition and coordination with bipy as sole ligand and anion are observed for the first time. Structure and composition are validated by X-ray diffraction based on single crystals and powders, XANES spectroscopy, infrared spectroscopy, and elemental analysis. Optical spectroscopy of the black-red, shiny metallic crystals shows absorption below 350 nm with a band gap <1.5 eV. Power–voltage curves indicate semiconducting behavior with a positive temperature gradient and silicon-like conductivity (3 × 10–4 S/m, 25 °C). In sum, the redox approach using Mn(0) nanoparticles allows for preparation of a Mn-coordinated interpenetrating network with 2,2′-bipy and 4,4′-bipy as sole ligands and semiconducting properties. ... mehrThe redox approach generally offers the option to realize further bipyridyl networks with other metals and semiconducting or metallic properties.