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

Author(s) Jo, H.; Ok, K.Min
Journal Chemistry
Date Published 2019 Dec 10

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-hisH )MoO F ] ⋅H O (L) and [(d-hisH )MoO F ] ⋅H O (D), and an achiral oxyfluoride, (l/d-hisH )MoO F (LD) (his=histidine, C H N O ) have been successfully self-assembled by a slow evaporation method. The structures of these compounds are composed of histidinium cations and distorted [MoO F ] octahedra. Surprisingly, the histidinium cations not only control macroscopic chirality, but also induce O/F ordering in MoO F 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 MoO F groups. Solid-state circular dichroism (CD) spectra indicate that the MoO F 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.

DOI 10.1002/chem.201903836
ISSN 1521-3765
Citation Chemistry. 2019;25(69):1587115878.

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