Paramagnetic Semiconducting Se-Mn Clusters: A Mn₃Se₄-Stabilized Selenide Radical Intermediate and Its Aggregated...

The transition metal-stabilized heavy main group radicals are extremely scarce due to their highly reactive natures, making them difficult to be isolated and identified. We report here a rare class of the Se radical-containing manganese carbonyl anionic cluster, [(μ-Se)(μ₃-Se₂)₂Mn₃(CO)₉]^•2- (1), which was successfully obtained from the one-pot reaction of Se powder and Mn₂(CO)₁₀ in concentrated KOH/MeOH/MeCN solutions at 90 °C. Dianion 1 and its dimeric cluster, [(μ₄-Se₂){(μ₃-Se₂)₂Mn₃(CO)₉}₂]^4- [(1)], could undergo the reversible Se-Se bond breakage or reformation by the thermal cracking of (1) or self-dimerization of 1, showing the μ-Se^•- radical character of 1. Complex 1 could react with (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) to form the Se radical-captured complex [(μ-Se(TEMPO)) (μ₃-Se₂)₂Mn₃(CO)₉]^2- (1-TEMPO) or could react with alkylene bromides (CH₂)Br₂ (n = 1, 2) to give the Mn₄-based oxidative coupling products, [(μ₄-Se₂)(μ-Se₂LSe)₂Mn₄(CO)₁₂]^2- (L = CH₂, 2-CH; Se, 2-Se). In addition, dianion 1 and its aggregated derivatives (1), 1-TEMPO, 2-CH, and 2-Se exhibited unusual paramagnetic properties with the spin-state switching from S = 1 (Mn) + 1/2 (Se) to S = 1 (Mn), in which their magnetic centers were proved to be mixed-valent Mn atoms and the μ-Se^•- radical, as evidenced by Evans method, superconducting quantum interference device, X-ray photoelectron spectra, electron paramagnetic resonance, and density functional theory calculations. Importantly, these clusters showed semiconducting behaviors with low and tunable energy gaps (1.50-2.01 eV) and varied electrical conductivities (2.52 × 10^-8-4.58 × 10^-9 S/cm), where efficient electron transports mainly arose from C-H(phenyl)···O(carbonyl) interactions within the solid-state frameworks.