Assembly of Metallacages into Soft Suprastructures with Dimensions of up to Micrometers and the Formation of Composite Materials

Abstract

This work provides a platform for the rapid generation of superstructure assemblies with a wide range of lengths that can be used to access a variety of metal–organic complex-based soft superstructures. Metallacage-based microneedles that are nanometers in diameter and millimeters in length were generated in dichloromethane and ethyl acetate; their size could be controlled by adjusting the ratio of the two solvents. Interestingly, microflower structures could be formed by further assembly of the microneedles during solvent evaporation. Our study establishes a feasible method designed to broaden the range of suprastructures with emissions from blue and green to red through the co-assembly of lysine-modified perylene. Similar to the co-assembly of lysine-modified perylene with microflowers, chlorophyll-a and vitamin B12 were introduced into the microflowers during the assembly process, which may be exploited in studies of energy capture and nerve repair in the future

Solvent-assisted coordination driven assembly of a supramolecular architecture featuring two types of connectivity from discrete nanocages

“…In general, the high symmetry of the MOC leads to a single type of nanocage building unit in most reported nanocage architectures 11,12. Interestingly, the nanocage of 1 exhibits high O h symmetry; moreover, two types of nanocage building units, nanocage building units A and B (Fig.…”

“…Until now, all of the reported studies have exhibited only the single node topology structures (4-c or 6-c nets) and the intermediate structure of these assembly processes remains a mystery 9. For most of the MOCs, their high symmetry11,12 restricts the generation of multiple connecting nodes, while multiple connectivity is essential for constructing complex hierarchical structures. To expand the possible complex architectures using one kind of nanocage reagent, multiple types of connectivity are needed for the nanocage building units, which has thus far remained challenging.…”

Recent progress and future challenges in the supramolecular polymerization of metal-containing monomers

“…Accordingly, coordination polymers 34 , metal organic frameworks 35,36 as well as the self-assembly of discrete metallomacrocycles/-cages [37][38][39][40][41] are out of the scope of this article. For the latter systems, recent relevant reports of metallomacrocycle/-cage-based SPs have been published, 42,43 but an adequate discussion of these systems would require a very comprehensive introduction to the fundamentals of their self-assembly prior to supramolecular polymerization. We refer the reader to excellent articles published elsewhere, which document recent progress of the field.…”

Tetraphenylethylene-Based Emissive Supramolecular Metallacages Assembled by Terpyridine Ligands

“…[35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50] In this field, Stang and co-workers 51 reported the first TPE-based supramolecular cage, which brought about the recent flourishing of AIE-active metalla-supramolecular cages with tunable properties. [52][53][54] Among most of these structures, the TPE moieties were either attached or embedded in the supramolecules, and their emissions still followed the classic AIE principle. Accordingly, high fluorescent efficiency was mainly observed in their aggregate state, in which the rotations of the benzene rings were restricted effectively.…”