4.8 Article

Supramolecular meso-Trick: Ambidextrous Mirror Symmetry Breaking in a Liquid Crystalline Network with Tetragonal Symmetry

期刊

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 144, 期 15, 页码 6936-6945

出版社

AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c01511

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资金

  1. National Natural Science Foundation of China [21774099, 21761132033, 11922410]
  2. Science and Technology Agency of Shaanxi Province [2016KW-050, 2018KWZ-03]
  3. German Research Foundation (DFG) [424355983, 436494874 -RTG 2670]
  4. China Scholarship Council (CSC) [201706280170]
  5. Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy [DE-AC02-05CH11231]

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A new stable chiral bicontinuous tetragonal liquid crystalline phase is reported as an intermediate phase during the transition between achiral double gyroid and chiral triple network cubic phases. The study reveals the mechanism of mirror symmetry breaking in soft matter during the transition process.
Bicontinuous and multicontinuous network phases are among nature's most complex structures in soft matter systems. Here, a chiral bicontinuous tetragonal phase is reported as a new stable liquid crystalline intermediate phase at the transition between two cubic phases, the achiral double gyroid and the chiral triple network cubic phase with an I23 space group, both formed by dynamic networks of helices. The mirror symmetry of the double gyroid, representing a meso-structure of two enantiomorphic networks, is broken at the transition to this tetragonal phase by retaining uniform helicity only along one network while losing it along the other one. This leads to a conglomerate of enantiomorphic tetragonal space groups, P4(1)2(1)2 and P4(3)2(1)2. Phase structures and chirality were analyzed by small-angle X-ray scattering (SAXS), grazing-incidence small-angle X-ray scattering (GISAXS), resonant soft X-ray scattering (RSoXS) at the carbon K-edge, and model-dependent SAXS/RSoXS simulation. Our findings not only lead to a new bicontinuous network-type three-dimensional mesophase but also reveal a mechanism of mirror symmetry breaking in soft matter by partial meso structure racemization at the transition from enantiophilic to enantiophobic interhelical self-assembly.

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