Shape-assisted self-assembly

Abstract

Self-assembly and molecular recognition are critical processes both in life and material sciences. They usually depend on strong, directional non-covalent interactions to gain specificity and to make long-range organization possible. Most supramolecular constructs are also at least partially governed by topography, whose role is hard to disentangle. This makes it nearly impossible to discern the potential of shape and motion in the creation of complexity. Here, we demonstrate that long-range order in supramolecular constructs can be assisted by the topography of the individual units even in the absence of highly directional interactions. Molecular units of remarkable simplicity self-assemble in solution to give single-molecule thin two-dimensional supramolecular polymers of defined boundaries. This dramatic example spotlights the critical function that topography can have in molecular assembly and paves the path to rationally designed systems of increasing sophistication.

Proton Affinity in the Chemistry of Beta-Octamolybdate: HPLC-ICP-AES, NMR and Structural Studies

“…Most self-assembly cascade reactions are pH driven when fast protonation-deprotonation processes provoke rapid species transformation/organization into various associates up to nanoscopic size. The study of self-assembly processes is one of the top subjects in modern chemical science [ 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 ]. Such a specific organization of the matter in different solutions is a research focus for a large number of research groups.…”

Self-Organization of Porphyrin–POM Dyads: Nonplanar Diacids and Oxoanions in Low-Dimensional H-Bonding Networks

“…Given the proximity of photonic reaction center, metallocluster, and a convenient reaction ‘pocket’ in the hexagonal porphyrin–POM net, such compounds could lead the way into new, photoactive ultrathin devices. Developing general principles for the relationship between individual molecular shape and intermolecular aggregation is a materials science frontier where significant progress is being achieved [ 59 ] and, given the shape-control mechanisms available, we see a promising future for porphyrin-bearing self-assembled materials.…”

Recent Concepts for Supramolecular 2D Materials

“…26 We have recently reported the first example of a saddle-shaped monomer able to self-assemble into monolayered 2D nanosheets of over 1 μm in length and single-molecule thickness from a solution of toluene (Figure 8). 27 This example showcases the impact topography can have to enforce order within assemblies through restriction of rotation and translation between monomers. The simplicity in the monomer design implies that association is primarily driven by p-p interactions and assisted by shape into 1D stacks, such that the individual effects alone would be insufficient.…”