Molecular recognition in biological systems plays a vital role in the precise construction of biomacromolecules and the corresponding biological activities. Such recognition mainly relies on the highly specific binding of complementary molecular pairs with complementary sizes, shapes, and intermolecular forces. It still remains challenging to develop artificial complementary motif pairs for coordination-driven self-assembly. Herein, a series of shape-dependent complementary motif pairs, based on ditopic 2,2':6',2″-terpyridine (TPY) backbone, are designed and synthesized. The fidelity degrees of self-assemblies from these motifs are carefully evaluated by multi-dimensional mass spectrometry, nuclear magnetic resonance spectroscopy, and molecular modeling. In addition, two levels of self-recognition in both homoleptic and heteroleptic assembly are discovered in the assembled system. Through finely tuning the shape and size of the ligands, a complementary pair is developed with error-free narcissistically self-sorting at two levels of self-recognition, and the intrinsic principle is carefully investigated.
Keywords: coordination-driven self-assembly; narcissistic self-sorting; shape-dependent self-recognition; terpyridine.
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