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Chaperone-like chiral cages for catalyzing enantio-selective supramolecular polymerization.

ABSTRACT: Cage catalysis has emerged as an important approach for mimicking enzymatic reactions by increasing the reaction rate and/or product selectivity of various types of covalent reactions. Here, we extend the catalytic application of cage compounds to the field of non-covalent molecular assembly. Acid-stable chiral imine cages are found to catalyze the supramolecular polymerization of porphyrins with an accelerated assembling rate and increased product enantioselectivity. Because the imine cages have a stronger interaction with porphyrin monomers and a weaker interaction with porphyrin assemblies, they can fully automatically detach from the assembled products without being consumed during the catalytic process. We reveal the kinetics of the auto-detachment of cages and the chirality growth of the assemblies using spectroscopic characterization studies. We find that the passivation groups attached to the cages are important for maintaining the structural stability of the cages during catalyzed assembly, and that the steric geometries of the cages can profoundly affect the efficiency of chiral regulation. This strategy demonstrates a new type of catalytic application of cage compounds in the field of molecular assembly, and paves the way to controlling supramolecular polymerization through a catalytic pathway.

SUBMITTER: Wang Y

PROVIDER: S-EPMC6910136 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

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Chaperone-like chiral cages for catalyzing enantio-selective supramolecular polymerization.

Wang Yu Y Sun Yibin Y Shi Peichen P Sartin Matthew M MM Lin Xujing X Zhang Pei P Fang Hongxun H Peng Pixian P Tian Zhongqun Z Cao Xiaoyu X

Chemical science 20190730 35

Cage catalysis has emerged as an important approach for mimicking enzymatic reactions by increasing the reaction rate and/or product selectivity of various types of covalent reactions. Here, we extend the catalytic application of cage compounds to the field of non-covalent molecular assembly. Acid-stable chiral imine cages are found to catalyze the supramolecular polymerization of porphyrins with an accelerated assembling rate and increased product enantioselectivity. Because the imine cages hav ...[more]

PMID: 31908753

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Project description:We report kinetically controlled chiral supramolecular polymerization based on ligand-metal complex with a 3 : 2 (L : Ag+) stoichiometry accompanying a helical inversion in water. A new family of bipyridine-based ligands (d-L1, l-L1, d-L2, and d-L3) possessing hydrazine and d- or l-alanine moieties at the alkyl chain groups has been designed and synthesized. Interestingly, upon addition of AgNO3 (0.5-1.3 equiv.) to the d-L1 solution, it generated the aggregate I composed of the d-L1AgNO3 complex (d-L1 : Ag+ = 1 : 1) as the kinetic product with a spherical structure. Then, aggregate I (nanoparticle) was transformed into the aggregate II (supramolecular polymer) based on the (d-L1)3Ag2(NO3)2 complex as the thermodynamic product with a fiber structure, which led to the helical inversion from the left-handed (M-type) to the right-handed (P-type) helicity accompanying CD amplification. In contrast, the spherical aggregate I (nanoparticle) composed of the d-L1AgNO3 complex with the left-handed (M-type) helicity formed in the presence of 2.0 equiv. of AgNO3 and was not additionally changed, which indicated that it was the thermodynamic product. The chiral supramolecular polymer based on (d-L1)3Ag2(NO3)2 was produced via a nucleation-elongation mechanism with a cooperative pathway. In thermodynamic study, the standard ΔG° and ΔH e values for the aggregates I and II were calculated using the van't Hoff plot. The enhanced ΔG° value of the aggregate II compared to that of the formation of aggregate I confirms that aggregate II was thermodynamically more stable. In the kinetic study, the influence of concentration of AgNO3 confirmed the initial formation of the aggregate I (nanoparticle), which then evolved to the aggregate II (supramolecular polymer). Thus, the concentration of the (d-L1)3Ag2(NO3)2 complex in the initial state plays a critical role in generating aggregate II (supramolecular polymer). In particular, NO3 - acts as a critical linker and accelerator in the transformation from the aggregate I to the aggregate II. This is the first example of a system for a kinetically controlled chiral supramolecular polymer that is formed via multiple steps with coordination structural change.

Dataset Information

Chaperone-like chiral cages for catalyzing enantio-selective supramolecular polymerization.

Publications

Chaperone-like chiral cages for catalyzing enantio-selective supramolecular polymerization.

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