Kinetic Control over Social and Narcissistic Self-Sorting from Multicomponent Mixtures in Seed-Initiated Supramolecular Polymerization by Fine-Tuning of Steric Effects.

Supramolecular polymers offer an intriguing possibility to transfer molecular properties from the nano- to the mesoscale. Towards this achievement, seed-initiated supramolecular polymerization has emerged as a powerful tool, as it prevents unlimited growth and enables size control of the assembly outcome. However, the potential application of the seeding method in the context of complex supramolecular systems is hitherto unclear. Herein we demonstrate that minute differences in molecular design in direct proximity to intermolecular recognition sites govern the molecular packing and in turn dictate the efficacy of seeded polymerization processes. We introduce a stepwise increase in steric demand in the central amino acid residue of a diamide system, which gradually increases the rotational displacement within the aggregated state. This fine-tuning of the molecular packing directly affects the propensity of the different aggregates to act as seeds for the other supramolecular synthons. In turn this allows us to selectively target specific trapped monomer states in binary mixtures for social or narcissistic seeded polymerization.

Shape-Dependent Complementary Ditopic Terpyridine Pair with Two Levels of Self-Recognition for Coordination-Driven Self-Assembly.

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.

Independent Blue and Red Light Triggered Narcissistic Self-Sorting Self-Assembly of Colloidal Particles.

The ability of living systems to self-sort different cells into separate assemblies and the ability to independently regulate different structures are one ingredient that gives rise to their spatiotemporal complexity. Here, this self-sorting behavior is replicated in a synthetic system with two types of colloidal particles; where each particle type independently self-assembles either under blue or red light into distinct clusters, known as narcissistic self-sorting. For this purpose, each particle type is functionalized either with the light-switchable protein VVDHigh or Cph1, which homodimerize under blue and red light, respectively. The response to different wavelengths of light and the high specificity of the protein interactions allows for the independent self-assembly of each particle type with blue or red light and narcissistic self-sorting. Moreover, as both of the photoswitchable protein interactions are reversible in the dark; also, the self-sorting is reversible and dynamic. Overall, the independent blue and red light controlled self-sorting in a synthetic system opens new possibilities to assemble adaptable, smart, and advanced materials similar to the complexity observed in tissues.

High-Fidelity, Narcissistic Self-Sorting in the Synthesis of Organometallic Assemblies from Poly-NHC Ligands.

Highly selective, narcissistic self-sorting has been observed in the one-pot synthesis of three organometallic molecular cylinders of type [M3 {L-(NHC)3 }2 ](PF6 )3 (M=Ag+ , Au+ ; L=1,3,5-benzene, triphenylamine, or 1,3,5-triphenylbenzene) from L-(NHC)3 and silver(I) or gold(I) ions. The molecular cylinders contain only one type of tris-NHC ligand with no crossover products detectable. Transmetalation of the tris-NHC ligands from Ag+ to Au+ in a one-pot reaction with retention of the supramolecular structures is also demonstrated. High-fidelity self-sorting was also observed in the one-pot reaction of benzene-bridged tris-NHC and tetrakis-NHC ligands with Ag2 O. This study for the first time extends narcissistic self-sorting in metal-ligand interactions from Werner-type complexes to organometallic derivatives.