Self-assembly, geometric and electronic structures, and structure-directing properties of organic–inorganic hybrid salt containing [WO2F4]2 − anions and protonated 2-(2-hydroxyphenyl)benzimidazole cations

One new organic–inorganic hybrid solid salt, [(pbmH)2] [WO2F4] (1) (pbm = 2-(2-hydroxyphenyl)benzimidazole), containing tungsten oxide fluoride anion [WO2F4]2 −, and organic cation, pbmH+, has been synthesized via solution-based self-assembling technique and characterized structurally. The geometric structure and electronic structure of [WO2F4]2 − anion have been calculated, and discussed in detail by the density functional theory levels (DFT), the partial density of states (PDOS) and the overlap population density of states (OPDOS) analyses. The experimental results are well comparable to those of theoretical ones. The observed crystal stacking and structure-directing properties of [WO2F4]2 − anion in crystalline 1 are well interpreted. Furthermore, the distortion of [WO2F4]2 − octahedron, the variation trend of bonding distances of Wsingle bondO/F atoms, and the structure-directing properties of [WO2F4]2 − anion, together with their inter-relationships have been well discussed.