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Sterics and Hydrogen Bonding Control Stereochemistry and Self-Sorting in BINOL-Based Assemblies.

ABSTRACT: Here we demonstrate how the hydrogen-bonding ability of a BINOL-based dialdehyde subcomponent dictated the stereochemical outcome of its subsequent self-assembly into one diastereomeric helicate form when bearing free hydroxy groups, and another in the case of its methylated congener. The presence of methyl groups also altered the self-sorting behavior when mixed with another, short linear dialdehyde subcomponent, switching the outcome of the system from narcissistic to integrative self-sorting. In all cases, the axial chirality of the BINOL building block also dictated helicate metal center handedness during stereospecific self-assembly. A new family of stereochemically pure heteroleptic helicates were thus prepared using the new knowledge gained. We also found that switching from Fe^II to Zn^II, or the incorporation of a longer linear ligand, favored heteroleptic structure formation.

SUBMITTER: Zou YQ

PROVIDER: S-EPMC8227477 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

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Sterics and Hydrogen Bonding Control Stereochemistry and Self-Sorting in BINOL-Based Assemblies.

Zou You-Quan YQ Zhang Dawei D Ronson Tanya K TK Tarzia Andrew A Lu Zifei Z Jelfs Kim E KE Nitschke Jonathan R JR

Journal of the American Chemical Society 20210614 24

Here we demonstrate how the hydrogen-bonding ability of a BINOL-based dialdehyde subcomponent dictated the stereochemical outcome of its subsequent self-assembly into one diastereomeric helicate form when bearing free hydroxy groups, and another in the case of its methylated congener. The presence of methyl groups also altered the self-sorting behavior when mixed with another, short linear dialdehyde subcomponent, switching the outcome of the system from narcissistic to integrative self-sorting. ...[more]

PMID: 34124891

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