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Histidinium‐Driven Chirality Control of Self‐Assembled Hybrid Molybdenum Oxyfluorides
Author(s) -
Jo Hongil,
Ok Kang Min
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201903836
Subject(s) - chirality (physics) , crystallography , octahedron , chemistry , circular dichroism , molybdenum , hydrogen bond , acentric factor , stereochemistry , materials science , crystal structure , inorganic chemistry , molecule , physics , chiral symmetry , organic chemistry , quantum mechanics , nambu–jona lasinio model , quark
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 ‐ his H 2 )MoO 2 F 4 ] 3 ⋅ H 2 O ( L ) and [( d ‐ his H 2 )MoO 2 F 4 ] 3 ⋅ H 2 O ( D ), and an achiral oxyfluoride, ( l / d ‐ his H 2 )MoO 2 F 4 ( LD ) ( his =histidine, C 6 H 9 N 3 O 2 ) have been successfully self‐assembled by a slow evaporation method. The structures of these compounds are composed of histidinium cations and distorted [MoO 2 F 4 ] 2− octahedra. Surprisingly, the histidinium cations not only control macroscopic chirality, but also induce O/F ordering in MoO 2 F 4 octahedra through hydrogen‐bonding interactions. Compounds L and D crystallize in the extremely rare polar space group P 1, and exhibit positive second harmonic generation (SHG) signals attributable to a net moment originating from the MoO 2 F 4 groups. Solid‐state circular dichroism (CD) spectra indicate that the MoO 2 F 4 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.