CrystEngComm_22_3_458_466.pdf 2.02 MB
Matsushima, Misaki Graduate School of Natural Science and Technology, Okayama University
Wada, Koki Graduate School of Natural Science and Technology, Okayama University
Takahara, Kazuma Graduate School of Natural Science and Technology, Okayama University
Sunatsuki, Yukinari Graduate School of Natural Science and Technology, Okayama University
Crystal structures and crystallisation behaviours of a series of first-row transition-metal(II) complexes bearing 1,1,1-tris[2-aza-3-(imidazol-4-yl)prop-2-enyl]ethane (H3L), [MII(H3L)]Cl(ClO4) (M = Mn, Fe, Co, Ni and Zn) were examined. These compounds crystallise in an orthorhombic crystal system with a non-enantiogenic (Sohncke) space group P212121, resulting in spontaneous resolution of the chiral complex cations. Hydrogen bonds between the imidazole N–H atoms in the tripodal ligand and chloride anions give enantiomorphic crystals with a homochiral three-dimensional network structure. In order to verify the spontaneous resolution of these compounds, solid-state circular dichroism spectra of the resulting single crystals were measured (KBr disk method). Unexpectedly, the observed spectra indicated that imbalanced formation of the enantiomorphic crystals (i.e., left-handed Λ-form vs. right-handed Δ-form complex cations) in all cases. Moreover, in the cases of NiII and ZnII compounds, predominant enantiomorphic crystals formed by spontaneous resolution were always the same (in at least ten of our recrystallisation experiments). These observations suggest that there is a certain (but as yet unknown) factor that affects the predominant deposition of either enantiomorphic crystal when spontaneous resolution takes place from a solution of a racemic mixture in which rapid racemisation occurs.
This fulltext is available in Dec. 2020.
Royal Society of Chemistry
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