Syntheses, structures, photoelectric properties and photocatalysis of iodobismuthate hybrids with lanthanide complex cations

Abstract

New iodobismuthate hybrids with lanthanide complex counter cations, [Ln(DMF)₈][Bi₂I₉] (Ln = La (1), Eu (2)) and [Tb(DMF)₈]₂[Bi₂I₉]₂ (3) (DMF = N,N-dimethylformamide), were prepared using solvated Ln(III) complexes formed in situ as structure-directing agents. The dimeric [Bi₂I₉]³⁻ anion moieties of compounds 1–3 are aggregated by two slightly twisted BiI₆ octahedra through face-sharing mode. The different crystal structures of 1–3 are due to the different I⋯I and C–H⋯I hydrogen bond interactions. Compounds 1–3 have narrow semiconducting band gaps at 2.23, 1.91 and 1.94 eV, respectively. Under Xe light irradiation, they exhibit steady photocurrent densities that are 1.81, 2.10 and 2.18 times higher than that of pure BiI₃, respectively. Compounds 2 and 3 exhibited higher catalytic activities than 1 in the photodegradation of organic dyes CV and RhB, which are attributed to the stronger photocurrent response derived from the redox cycles of Eu³⁺/Eu²⁺ and Tb⁴⁺/Tb³⁺.