Benzene-1,4-Di(dithiocarboxylate) Linker-Based Coordination Polymers of Mn²⁺, Zn²⁺, and Mixed-Valence Fe^2+/3+

Three new coordination polymers (CPs) constructed from the linker 1,4-di(dithiocarboxylate) (BDDTC^2-)─the sulfur-analog of 1,4-benzenedicarboxylate (BDC^2-)─together with Mn-, Zn-, and Fe-based inorganic SBUs are reported with description of their structural and electronic properties. Single-crystal X-ray diffraction revealed structural diversity ranging from one-dimensional chains in [Mn(BDDTC)(DMF)₂] (1) to two-dimensional (2D) honeycomb sheets observed for [Zn₂(BDDTC)₃][Zn(DMF)₅(H₂O)] (2). Gas adsorption experiments confirmed a 3D porous structure for the mixed-valent material [Fe₂(BDDTC)₂(OH)] (3). 3 contains a 1:1 ratio of Fe^2+/3+ ions, as evidenced by ⁵⁷Fe Mössbauer, X-band EPR, and X-ray absorption spectroscopy. Its empirical formula was established by elemental analysis, thermal gravimetric analysis, infrared vibrational spectroscopy, and X-ray absorption spectroscopy in lieu of elusive single-crystal X-ray diffraction data. In contrast to the Mn- and Zn-based compounds 1 and 2, the Fe^2+/3+ CP 3 showed remarkably high electrical conductivity of 5 × 10^-3 S cm^-1 (according to van der Pauw measurements), which is within the range of semiconducting materials. Overall, our study confirms that sulfur derivatives of typical carboxylate linkers (e.g., BDC) are suitable for the construction of electrically conducting CPs, due to acceptedly higher covalency in metal-ligand bonding compared to the electrically insulating carboxylate CPs or metal-organic frameworks. At the same time, the direct comparison between insulating CPs 1 and 2 with CP 3 emphasizes that the electronic structure of the metal is likewise a crucial aspect to construct electrically conductive materials.