Strong Photocurrent Response of Selenoarsenates With Different Transition Metal Complexes as Structure-Directing Agents

Abstract

Four selenoarsenates with different transition-metal complexes [Co(tren)₂H]AsSe₄ [tren = tris(2-aminoethyl)amine] (1); [Ni₂(dien)₄](As₂Se₅) (dien = diethylenetriamine) (2); [Zn(tren)]₂(As₂Se₅) (3) and [Mn(tren)]₂(As₂Se₅) (4) were solvothermally synthesized in a mixed solvent of organic amine and alcohol solution. The compounds 1-4 have pyramidal/tetrahedral structures (AsSe₃/AsSe₄), and contain transition metal (Co²⁺, Ni²⁺, Zn²⁺ and Mn²⁺) complex that form distinct zero-dimensional (0-D) clusters. Arsenic atoms form a tetrahedron in compounds 1 and 2; 1 consists of discrete tetrahedral (AsSe₄) and transition metal complex [Co(tren)₂]²⁺; 2 is composed of an anion [As₂Se₅]^4- cluster and transition metal complex [Ni(dien)₂]²⁺. In compounds 3 and 4, arsenic atom forms a pyramidal AsSe₃ and the two pyramidal AsSe₃ share a corner connection to form a dimer [As₂Se₅]^4-; 3 is characterized as a cluster consisting of two unsaturated [Zn(tren)]²⁺ caiton linked by a dimer (As₂Se₅)^4- linkage; in 4, unsaturated [Mn(tren)]²⁺ caiton is linked to two trigonal-bipyramidal [Mn(tren)]Se via dimer (As₂Se₅)^4- to form [Mn(tren)]₄[As₄Se₁₀] cluster. To our knowledge, [Zn(tren)]₂(As₂Se₅) (3) is the first zinc selenoarsenate containing the (As₂Se₅)^4- anion type. Furthermore, the Mn²⁺ ions adopt a trigonal-biyramidal (five-coordinate) and octahedral (six-coordinate) environment. Adding K₂CO₃/Cs₂CO₃ to the synthesis system is necessary and may act as a mineralizer. Several properties of compounds 1-4 have been characterized in our studies, in particular their strong photocurrent response characteristics under visible light irradiation.

Keywords: crystal structure; photocurrent responses; selenoarsenates; solvothermal method; transition metal complex.