In this study, a preferential trans configuration with the assistance of the steric hindrance effect was demonstrated in a dynamic covalent reaction between 2-pyridyl hydrazide and 2-pyridyl aldehyde. By employing the dynamic covalent reaction between dihydrazide and dialdehyde, a type of self-folding helical dynamic covalent polymer was created by spontaneous configuration control. The helical polymers possess folding-directed hollow tubular structures and thus are capable of providing a specific microenvironment for catalyzing the thiol-related oxidation reaction in the presence of hydrogen peroxide.
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