2019
DOI: 10.1021/jacs.8b12323
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Hydrogen-Bond-Assisted Symmetry Breaking in a Network of Chiral Metal–Organic Assemblies

Abstract: Herein we elucidate the interplay of chiral, chelate, solvent and hydrogen-bonding information in the self-assembly of a series of new three-dimensional metal-organic architectures. Enantiopure ligands, each containing H-bond donors and acceptors, form different structures depending on the ratio in which they are combined: enantiopure components form M4L4 assemblies, whereas racemic mixtures form M3L3 stacks. Chiral amplification within M3L3 enantiomers was observed when a 2:1 ratio of R and S subcomponent ena… Show more

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Cited by 40 publications
(22 citation statements)
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“…[1][2][3] The construction principles of such architectures take into account the symmetries of their subunits, which must connect in such a way to generate the overall superstructure. Coordinative and ligand stereochemistries also impact upon structure, [4][5][6][7][8][9][10][11][12][13][14][15] although controlling these design elements can be challenging. 16,17 For example, the factors that affect the stereochemical conguration of ligands around octahedral metal ions in the assembly of discrete three-dimensional architectures are complex.…”
Section: Introductionmentioning
confidence: 99%
“…[1][2][3] The construction principles of such architectures take into account the symmetries of their subunits, which must connect in such a way to generate the overall superstructure. Coordinative and ligand stereochemistries also impact upon structure, [4][5][6][7][8][9][10][11][12][13][14][15] although controlling these design elements can be challenging. 16,17 For example, the factors that affect the stereochemical conguration of ligands around octahedral metal ions in the assembly of discrete three-dimensional architectures are complex.…”
Section: Introductionmentioning
confidence: 99%
“…Asymmetrical binding environments can also be created through heteroleptic assembly, wherein multiple different building blocks combine to generate a single entity. 17,[30][31][32][33][34][35][36][37][38][39] The bringing together of multiple components into one specific configuration, from among other possibilities, usually incurs an entropic penalty. The selective synthesis of heteroleptic structures is thus often designed to be enthalpically favorable, as strain within homoleptic derivatives is avoided upon formation of a mixed-ligand system.…”
Section: Introductionmentioning
confidence: 99%
“…The dynamic nature of many transition metal–ligand interactions, characterized by precise geometry and directionality, combined with a polytopic ligand structure, allow us to design and self-assemble a plethora of compounds with different shapes, sizes, and properties. Embedded functions, depending on either individual building blocks or their synergistic interaction, may involve host–guest interactions, photoswitching, , chirality, chromophore effects, or catalysis, just to name a few.…”
mentioning
confidence: 99%