Incorporating transition metal complexes into tetrathioarsenates(V): syntheses, structures, and properties of two unprecedented [Mn(dien)2]n[Mn(dien)AsS4]2n.4nH2O and [Mn(en)3]2[Mn(en)2AsS4][As3S6].

Two transition-metal tetrathioarsenate complexes, [Mn(dien)(2)](n)[Mn(dien)AsS(4)](2n).4nH(2)O (1) with one-dimensional water chain and [Mn(en)(3)](2)[Mn(en)(2)AsS(4)][As(3)S(6)] (2) with mixed-valence As(3+)/As(5+) character, have been synthesized and structurally characterized. The tetrathioarsenate(V) anion acts as a novel mu(2)-eta(1),eta(2) ligand in 1 and as a chelating ligand in 2. The two compounds exhibit intriguing semiconducting properties (E(g) = 2.18 eV (1), 2.48 eV (2)) and strong photoluminescence with the emission maximum occurring around 440 nm.