Manganese Telluride Carbonyl Complexes: Facile Syntheses and Exotic Properties - Reversible Transformations, Hydrogen Generation, Paramagnetic, and Semiconducting Properties

A novel family of five Mn-Te-CO complexes was prepared via facile syntheses: mono spirocyclic [Mn₄Te(CO)₁₆]^2- (1), four-membered Mn₂Te₂ ring-type [Mn₂Te₂(CO)₈]^2- (2), hydride-containing square pyramidal [HMn₃Te₂(CO)₉]^2- (3), and dumbbell-shaped [Mn₆Te₆(CO)₁₈]^4- (4) and [Mn₆Te₁₀(CO)₁₈]^4- (5). Electron-precise complexes 4 and 5 exhibit unusual paramagnetism arising from two types of Mn atoms in different oxidation states, as determined by X-ray photoelectron spectroscopy, electron paramagnetic resonance, and density functional theory (DFT) calculations. The structural transformations from small-sized Mn₄Te 1 and Mn₂Te₂ 2 to the largest Mn₆Te₁₀ 5 were controllable, the off/on magnetic-switched transformation between HMn₃Te₂ 3 and 5 was reversible, and the magnetic transformation between Mn₆Te₆ 4 and 5 was observed. Interestingly, the reversible dehydridation and hydridation between the HMn₃Te₂-based cluster 3 and [Mn₃Te₂(CO)₉]^- were successfully accomplished, in which the release of a high yield of H₂ was detected by gas chromatography. In addition, upon the addition of CO, cluster 3 first forms a carbonyl-inserted intermediate [HMn₃Te₂(CO)₁₀]^2- (3′), detected by the high resolution ESI-MS, which is readily transformed to a dimeric dihydrido cluster [{HMn₃Te₂(CO)₁₀}₂]^2- (6) with the introduction of O₂. These low- to high-nuclearity complexes exhibit rich redox properties with semiconducting behavior in solids, possessing low but tunable energy gaps (1.06-1.62 eV) due to efficient electron transport via nonclassical C-H···O(carbonyl) interactions. The structural nature, reversible structural transformations, controllable on/off magnetic switches, electron communication networks, and associated chemical properties for hydrogen generation are discussed in detail and supported by DFT calculations, density of states, band structures, and noncovalent interaction analyses.