Photochargeable Mn-Based Metal-Organic Framework and Decoupled Photocatalysis.

Designing multifunctional materials that mimic the light-dark decoupling of natural photosynthesis is a key challenge in the field of energy conversion. Herein, we introduce MnBr-253, a precious metal-free metal-organic framework (MOF) built on Al nodes, bipyridine linkers and MnBr(CO)3(bipyridine) complexes. Upon irradiation, MnBr-253 colloids demonstrate an electron photocharging capacity of ~42 C ⋅ g-1 MOF, with state-of-the-art photocharging rate (1.28 C ⋅ s-1 ⋅ g-1 MOF) and incident photon-to-electron conversion efficiency of ~9.4 % at 450 nm. Spectroscopic and computational studies support effective electron accumulation at the Mn complex while high porosity and Mn loading account for the notable electron storage performance. The charged MnBr-253 powders were successfully applied for hydrogen evolution under dark conditions thus emulating the light-decoupled reactivity of photosynthesis.

Benzene-1,4-Di(dithiocarboxylate) Linker-Based Coordination Polymers of Mn2+, Zn2+, and Mixed-Valence Fe2+/3.

Three new coordination polymers (CPs) constructed from the linker 1,4-di(dithiocarboxylate) (BDDTC2-)─the sulfur-analog of 1,4-benzenedicarboxylate (BDC2-)─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 Fe2+/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 Fe2+/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.