α- to β-[C 6H 4(NH 3) 2] 2Bi 2I 10 reversible solid-state transition, thermochromic and optical studies in the p-phenylenediamine-based iodobismuthate(III) material

Abstract

α-[C 6H 4(NH 3) 2] 2Bi 2I 10, which is a new material containing low-dimensional iodobismuthate anions, was synthesized and through its single crystal X-ray diffraction measurements, was proven to crystallize at room temperature in the centrosymmetric space group P2 1 /c. It consists of a p-phenylenediammonium dication and a discrete (0-D) anion built up of edge-sharing bioctahedron. Due to the hydrogen bonds and the interatomic distances (Bi–I, I⋯I and π–π) changes, α-phase was transformed into the corresponding centrosymmetric β-phase, β-[C 6H 4(NH 3) 2] 2Bi 2I 10, through a single-crystal to single-crystal transformation occurring upon cooling to −28/−26 °C. Below the transition temperature, β-[C 6H 4(NH 3) 2] 2Bi 2I 10 crystallizes in the monoclinic system, centrosymmetric space group P2 1 /n. Besides, the optical transmission measurements on α-[C 6H 4(NH 3) 2] 2Bi 2I 10 thin films have revealed two absorption bands at 2.47 and 3.01 eV. Finally, two room temperature photoluminescence emissions attributed to excitons radiative recombinations confined within the bioctahedra Bi 2I 10 4−, were observed in the red spectral range at 1.9 and 2.05 eV energy.