Histidinium-Driven Chirality Control of Self-Assembled Hybrid Molybdenum Oxyfluorides

Exploring macroscopic chiral materials with extended structures has become an important and fundamental topic in chemistry. To systematically control the chirality of novel organic-inorganic frameworks, histidinium-based cationic structure-directing agents containing specific chiral information are introduced. In this way, two chiral compounds, [(l-hisH₂ )MoO₂ F₄ ]₃ ⋅H₂ O (L) and [(d-hisH₂ )MoO₂ F₄ ]₃ ⋅H₂ O (D), and an achiral oxyfluoride, (l/d-hisH₂ )MoO₂ F₄ (LD) (his=histidine, C₆ H₉ N₃ O₂ ) have been successfully self-assembled by a slow evaporation method. The structures of these compounds are composed of histidinium cations and distorted [MoO₂ F₄ ]^2- octahedra. Surprisingly, the histidinium cations not only control macroscopic chirality, but also induce O/F ordering in MoO₂ F₄ octahedra through hydrogen-bonding interactions. Compounds L and D crystallize in the extremely rare polar space group P1, and exhibit positive second harmonic generation (SHG) signals attributable to a net moment originating from the MoO₂ F₄ groups. Solid-state circular dichroism (CD) spectra indicate that the MoO₂ F₄ units templated by histidinium cations are chirally aligned through ionic interactions. Crystallization processes influenced by the chirality of the reported materials are also discussed herein.