Chiral Symmetry Breaking by Chemically Manipulating Statistical Fluctuation in Crystallization

Wu, Shuting; Wu, Yan-Rong; Kang, Qing‐Qing; Zhang, Hui; Liu, Long; Zheng, Zhiping; Huang, Rong‐Bin; Zheng, Lan‐Sun

doi:10.1002/ange.200703443

Cited by 21 publications

(9 citation statements)

References 52 publications

(19 reference statements)

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“…There are two families of refcodes within the qzd MOF cluster: LIWDEB (13 occurrences) and UKUVOL (21 occurrences). 58,59 All of these structures are one of two isomers of [{Cu(succinate)(4,4bipyridine)} n ], isolated under different experimental conditions, and thus could be considered duplicates. The high geometric similarity between duplicates relative to the similarity between other structures in the dataset skews the representation towards creating an isolated cluster.…”

Section: Embedding Schemesmentioning

confidence: 99%

Visualization and Quantification of Geometric Diversity in Metal–Organic Frameworks

Nicholas

Alexandrov

Блатов

et al. 2021

Preprint

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With ever-growing numbers of metal-organic framework (MOF) materials being reported, new computational approaches are required for a quantitative understanding of structureproperty correlations in MOFs. Here we show how structural coarse-graining and embedding ("unsupervised learning") schemes can together give new insight into the geometric diversity of MOF structures. Based on a curated dataset of 1,262 reported experimental structures, we automatically generate coarse-grained and rescaled representations which we couple to a kernel-based similarity metric and to widely used embedding schemes. This approach allows us to visualize the breadth of geometric diversity within individual topologies, and to quantify the distributions of local and global similarities across the structural space of MOFs. The methodology is implemented in an openly available Python package, and is expected to be useful in future high-throughput studies.

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Section: Embedding Schemesmentioning

confidence: 99%

Visualization and Quantification of Geometric Diversity in Metal–Organic Frameworks

Nicholas

Alexandrov

Блатов

et al. 2021

Preprint

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“…This phenomenon indicated that the preferred handedness of aggregates was governed by chance, not by any possible external chiral impurities in the system. 39,50 We then tested the heating temperature on the self-assembly of OPV 3 -b-PEG 17 in the mixture of water/ethanol (v/v = 1/1). OPV 3 -b-PEG 17 solution samples (0.1 mg/mL) were heated at 40, 55, and 70 °C, respectively, for 1 h followed by aging at room temperature (23 °C) for 48 h. Irregular platelets were formed upon heating at 40 °C and the solution showed very weak Cotton effect (Figure 3A,D).…”

Section: Different Conditionsmentioning

confidence: 99%

“…At the initial stage of the formation of aggregates driven by π−π stacking of OPV 3 segments accompanying with possible steric repulsion between solvated PEG domains, the occurrence of statistical fluctuations in the orientation of ordered packing of OPV 3 blocks could lead to an accidental excess of helical or/and twisted structures. 39,50 Because of the strong directional interaction deriving from π−π stacking between OPV 3 segments, the growth of aggregates by addition of free OPV 3 -b-PEG 17 onto the ends of existed helical or twisted "seeds" of aggregates preferred to follow the same direction. 52 Besides, once a certain helical sense excess exists, the newly formed aggregates might follow the same direction, rather than opposite helical or twisted direction, by chiral autocatalysis.…”

Section: Different Conditionsmentioning

confidence: 99%

Self-Assembled Helical and Twisted Nanostructures of a Preferred Handedness from Achiral π-Conjugated Oligo(p-phenylenevinylene) Derivatives

et al. 2019

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The formation of chiral nanostructures from the self-assembly of achiral building blocks without external symmetry breaking inducing factors is believed to associate with the origin of chirality. Herein, we reported the synthesis and self-assembly of oligo(p-phenylenevinylene)-b-poly(ethylene glycol) (OPV3-b-PEG17, the subscripts represent the number of repeat unit of each block) in solution. We systematically examined the influence of solvent, heating temperature, and concentration of OPV3-b-PEG17 on the self-assembly of OPV3-b-PEG17 by UV/vis absorption and fluorescence spectrometry, circular dichroism technique, and transmission electron and atomic force microscopy. Interestingly, helical and twisted nanoribbons and nanotubes of a preferred handedness can be formed from achiral OPV3-b-PEG17 in the mixture of water/ethanol (v/v = 1/1) and the solution showed an obvious exciton-coupled bisignated signal, which indicated that symmetry breaking occurred during the formation of these nanostructures without external inducing factors. Our results showed that the occurrence of symmetry breaking is subtle to the experimental factors including solvent, heating temperature, and concentration of OPV3-b-PEG17. The directional π–π stacking along with steric repulsion between PEG domains should be the driving force for the formation of these chiral nanostructures. The occurrence of statistical fluctuations in the initial stage of self-assembly led to an accidental excess of helical or/and twisted structures, that is, symmetry breaking. Subsequently, the autocatalysis effect resulted in the formation of helical or/and twisted nanoribbons with a preferred handedness.

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“…24−29 The spontaneous resolution of chiral MOFs from achiral precursors usually results in conglomerates, i.e., a mixture of homochiral crystals having opposite handedness. 30 However, the generation of homochirality from achiral precursors is still unpredictable. Various factors such as coordination around the metal center, selection of the ligands, and host−guest interactions and stacking interactions can maneuver the formation of chiral MOFs from achiral building blocks.…”

Section: ■ Introductionmentioning

confidence: 99%

Spontaneous Resolution and Structure Transformation of Ni^II Metal–Organic Frameworks from an Achiral Precursor

Tao

Yang

Han

et al. 2019

Crystal Growth & Design

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Metal-center-driven spontaneous resolution of a pair of chiral doubly interpenetrated metal−organic frameworks (MOFs), [Ni 3 (ptd) 6 ]• 15.5H 2 O (1), which was synthesized from achiral precursors [ptd = 3-(pyridin-3-yl)-1,2,4-triazine-5,6-diol], shows vertical interpenetrated 2D → 3D frameworks with 1D channels. Interestingly, proceeding with solvothermal recrystallization in methanol, 1, with a high-symmetry tetragonal I4 space group, gives another tilted interpenetrated MOF of [Ni 3 (ptd) 2), with low-symmetry monoclinic C2 space group. Accompanied with the structure transformation, a red shift in circular dichroism (CD) spectrum and a magnetic response (weak ferromagnetic interactions in 1 to weak antiferromagnetic interactions in 2) can be observed. Strikingly, 1 and 2 feature heterogeneous catalytic activities for the Knoevenagel reaction.

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Chiral Symmetry Breaking by Chemically Manipulating Statistical Fluctuation in Crystallization

Cited by 21 publications

References 52 publications

Visualization and Quantification of Geometric Diversity in Metal–Organic Frameworks

Visualization and Quantification of Geometric Diversity in Metal–Organic Frameworks

Self-Assembled Helical and Twisted Nanostructures of a Preferred Handedness from Achiral π-Conjugated Oligo(p-phenylenevinylene) Derivatives

Spontaneous Resolution and Structure Transformation of Ni^II Metal–Organic Frameworks from an Achiral Precursor

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Chiral Symmetry Breaking by Chemically Manipulating Statistical Fluctuation in Crystallization

Cited by 21 publications

References 52 publications

Visualization and Quantification of Geometric Diversity in Metal–Organic Frameworks

Visualization and Quantification of Geometric Diversity in Metal–Organic Frameworks

Self-Assembled Helical and Twisted Nanostructures of a Preferred Handedness from Achiral π-Conjugated Oligo(p-phenylenevinylene) Derivatives

Spontaneous Resolution and Structure Transformation of NiII Metal–Organic Frameworks from an Achiral Precursor

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Spontaneous Resolution and Structure Transformation of Ni^II Metal–Organic Frameworks from an Achiral Precursor