Linkage control between molecular and supramolecular chirality in 2₁-helical hydrogen-bonded networks using achiral components.

Linkage control between molecular and supramolecular chirality in 2₁-helical hydrogen-bonded networks using achiral components.
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DOI:
10.1038/ncomms2756
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发表时间:
2013
影响因子:
16.6
通讯作者:
--
中科院分区:
综合性期刊1区
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--
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Chiral molecules preferentially form one-handed supramolecular assemblies that reflect the absolute configuration of the molecules. Under specific conditions, however, the opposite-handed supramolecular assemblies are also obtained because of flexibility in the bond length and reversibility of non-covalent interactions. The mechanism of the handedness selectivity or switching phenomenon remains ambiguous, and most phenomena are observed by chance. Here we demonstrate the construction of chiral hydrogen-bonded twofold helical assemblies with controlled handedness in the crystalline state based on crystallographic studies. Detailed investigation of the obtained crystal structures enabled us to clarify the mechanism, and the handedness of the supramolecular chirality was successfully controlled by exploiting achiral factors. This study clearly reveals a connection between molecular chirality and supramolecular chirality in the crystalline state. Chiral molecules form one-handed supramolecular assemblies but may be induced to switch to the other handed assembly, although the mechanisms driving these processes are unclear. Here, the authors demonstrate control of the supramolecular assembly handedness via the introduction of achiral counter ions.
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