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

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)_nNH₃⁺ based on structural data and V/Z variation with (CH₂)_n chains (n = 2–8, 12), and variation of BiCl₆³⁻ Raman frequencies modes versus (CH₂)_n chains (n = 3–8). Hydrate salts with (n = 3, 12) consist of isolated BiCl₆³⁻ anions and two water molecules, against others ones with isolated anionic chains [BiCl₅²⁻]_n or Bi₂Cl₁₀⁴⁻ dimers, formed by distorted octahedra BiCl₆³⁻ 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)_nNH₃BiCl₅ (n = 5–7) salts were used as highly efficient catalysts, which is a novel tendency in chlorobismuthate researchs in the green chemistry field. [ABSTRACT FROM AUTHOR]