Recent advances on structural, thermal, vibrational, optical, phase transitions, and catalysis properties of alkylenediammonium halogenometallate materials (Metal: Bi, Sb, Halogen: Cl, Br, I)

Abstract

Abstract This paper aims to review recent advances on synthesis, crystal structures, thermal, spectroscopic, phase transitions, optical, dielectric, and catalysis properties of hydrate and anhydrous alkylenediammonium halogenometallates materials (Metal: Bi, Sb, Halogen: Cl, Br, I). These hybrid materials present rich structural diversities based on octahedra forming infinite zero dimensional, 1-dimensional chains, 2-dimensional layers, discrete bioctahedra, and discrete tetramer units. The effect, contribution and importance of hydrogen bonding N–H … X (X: Cl, Br, I) are reviewed in terms of solid state relationship. Particularly, a comparative study is made on hydrate and anyhdrous aliphatic chlorobismuthates with alkylenediammonium +NH3(CH2) n NH3 + based on structural data and V/Z variation with (CH2) n chains (n = 2–8, 12), and variation of BiCl6 3− Raman frequencies modes versus (CH2) n chains (n = 3–8). Hydrate salts with (n = 3, 12) consist of isolated BiCl6 3− anions and two water molecules, against others ones with isolated anionic chains [BiCl5 2−] n or Bi2Cl10 4− dimers, formed by distorted octahedra BiCl6 3− sharing corners, vices or edges. The reviewed optical and electronic band gaps suggested interesting compounds with band gaps (1.85–2.4 eV), as suitable materials in optoelectronic properties, photoactive layer in solution-processed photovoltaics, and bio-imaging or photovoltaic applications. It was concluded that iodobismuthate salts have generally the lowest bands gap, compared to that of bromo and chlorobismuthate slats. Catalysis proprieties are reviewed n fast (RhB) degradation under dark conditions for (C4N2H7)4Bi2Cl10, (C5H9N2)BiI4, and {(H-BPA)4·[(BiI6)I13]·2I3} n , and in organic salts synthesis under solvent-free conditions. Herein NH3(CH2) n NH3BiCl5 (n = 5–7) salts were used as highly efficient catalysts, which is a novel tendency in chlorobismuthate researchs in the green chemistry field.