Syntheses, paramagnetism, and semiconducting characteristics of polynuclear manganese carbonyl chalcogenide anions: A review

The chemistry of manganese−chalcogenide clusters has attracted extensive attention due to their versatile syntheses, unique structures, and potential applications in magnetic and semiconducting materials. In this short account, we will review our recent progress in the chemistry of Mn₂-, Mn₃-, Mn₄-, and Mn₆-based manganese carbonyl chalcogenide (Se, Te) cluster anions, in which their facile one-pot syntheses, reversible structural transformations, and unique chemical and physical properties were described. These E−Mn−CO (E = Se, Te) cluster anions were found to react with O₂, alkylene bromides, strong acids, or even CO, giving various oxidative or functionalized Mn₃-, Mn₄-, and Mn₆-based paramagnetic tellurides or selenides derivatives. These manganese carbonyl selenides or tellurides exhibited semiconducting behaviors with tunable energy gaps and moderate electrical conductivities. Their efficient electron communication was mainly attributed to the weak interactions between cluster anions and cations, which were further investigated with DFT calculations.