Solvothermal Synthesis, Crystal Structures, and Photocatalytic Properties of Iodoplumbate Hybrids with Nickel(II) Complex Templates

Abstract

Organic–inorganic iodoplumbate hybrids [Ni(en)2]2Pb3I10 (1), [Ni(en)3]Pb2I6 (2) (en = ethylenediamine), [Ni(dien)2]Pb2I6·H2O (3) (dien = diethylenetriamine), [Ni(14‐TMC)][PbI3]2·DMF (4), and [Ni(14‐TMC)]2[Pb5I14(DMSO)2] (5) (14‐TMC = 1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclotetradecane) were prepared using different NiII complex cation as structural directing agents under solvothermal conditions. Compounds 1–4 consist of 1‐D [Pb3I104–]n, [PbI3–]n and [Pb2I62–]n polymeric anions constructed by PbI6 octahedra via corner‐, edge‐ or face‐sharing, respectively. The novel organic hybrid iodoplumbate anion [Pb5I14(DMSO)24–]n in 5 is composed of PbI6 and PbI5O octahedra via edge‐ and face‐sharing. The formation of polymeric iodoplumbate anions in 1–5 indicates different structure‐directing effect of the NiII complex cations with various polyamino ligands under appropriate reaction and crystallization conditions. Compounds 1–5 exhibit tunable band gaps varying in the range of 2.18–2.61 eV. Compounds 4 and 5 are more effective than 1 and 3 in the photocatalytic degradation of methylene blue.