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

• A series of Mn 2 -, Mn 3 -, Mn 4 -, and Mn 6 -based manganese carbonyl chalcogenide (Se, Te) cluster anions were synthesized via one-pot reactions of chalcogen powders and Mn 2 (CO) 10 with the absence or presence of metathesis salts in basic solutions. • These E −Mn−CO (E = Se, Te) clusters could undergo structural transformation, dioxygen activation, se radical coupling, alkylene bromide functionalization, hydride removal/addition, or oxidative carbonylation to produce a series of functionalized or oxidative products. • The Mn 3 -, Mn 4 -, and Mn 6 -based selenides or tellurides were found to have paramagnetic properties with S = 1 or S = 1 + 1/2 for the se radical-containing Mn 3 cluster. • The rare manganese chalcogenide cluster anions revealed low-energy-gap semiconducting characteristics, which were well-elucidated with DFT calculations. 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 Mn 2 -, Mn 3 -, Mn 4 -, and Mn 6 -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 O 2 , alkylene bromides, strong acids, or even CO, giving various oxidative or functionalized Mn 3 -, Mn 4 -, and Mn 6 -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. This mini-review showcases our recent progress on the chemistry of selenium- or tellurium-containing manganese carbonyl cluster anions regarding their syntheses, structures, and reactivities. Their intriguing O 2 /Se 8 activation, Se radical coupling, alkylene bromide functionalization, hydride removal/addition, and oxidative carbonylation were demonstrated. Their unexpected paramagnetism and semiconductivities were also illustrated. [Display omitted] [ABSTRACT FROM AUTHOR]