Solvothermal Synthesis and Characterization of One‐dimensional Indium Polyselenides with Transition Metal Complexes

Two different systems were used for syntheses of metal selenides, [Mn(en) 3 ][In 2 Se 5 ] ( 1 ) and [MnSe(en) 0.5 ] ( 2 ) by the reactions of In 2 Se 3 , MnCl 2 , and selenium powder at 170 °C for 6 days. Compound 1 contains a one‐dimensional [In 2 Se 5 ] 2– chain propagating along the crystallographic c axis separated by [Mn(en) 3 ] 2+ complex cations. The anionic chain is constructed by vertex‐linked InSe 4 tetrahedra linked by Se–Se bridges and contains four‐membered [In 2 Se 2 ] rings and five‐membered [(In 3+ ) 2 (Se 2 2– )(Se 2– )] rings. Compound 2 has a three‐dimensional network containing a monolayer of [MnSe] slabs, which is interconnected by bridging en linkers. The [MnSe] slab is a puckered 6 3 (honeycomb) net formed by alternating three‐coordinate manganese and selenium atoms.