Strategies to create hierarchical self-assembled structures via cooperative non-covalent interactions

Abstract

Cooperative phenomena are common processes involved in the hierarchical self-assembly of multiple systems in nature, such as the tobacco mosaic virus and a cell's cytoskeleton. Motivated by the high degree of order exhibited by these systems, a great deal of effort has been devoted in the past two decades to design hierarchical supramolecular polymers by combining different classes of cooperative interactions. In this review, we have classified the field of supramolecular polymers depending on the cooperative non-covalent forces driving their formation, with particular emphasis on recent examples from literature. We believe that this overview would help scientists in the field to design novel self-assembled systems with improved complexity and functionalities.

Control over the Self‐Assembly Modes of PtII Complexes by Alkyl Chain Variation: From Slipped to Parallel π‐Stacks

“…19 The presence of an extended aromatic surface in 2 anticipates that strong π−π interactions will be a major contribution to the supramolecular polymerization. According to literature precedent, we hypothesized that either metal•••metal 53 or weak interactions 52 involving the Cl-Pt(II)-Cl fragment of 2 could represent additional forces to the cooperative growth.…”

“…[5][6][7][8][9][10][11][12][13][14][15][16][17] In order to achieve these functionalities, highlyordered, adaptive nanostructures formed via a cooperative supramolecular polymerization mechanism are highly desirable. 18 The introduction of orthogonal noncovalent interactions, 19 from which hydrogen bonding and combinations with other secondary interactions are by far the most exploited ones, 20 represents a rational means for this purpose. The majority of these systems include purely organic building blocks, whereas the role of metal ions and polarized metal-bound atoms has been explored to a much lesser extent.…”

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

“…Of course, the full realm of non-covalent interactions is far vaster. As an example, today the importance of both cooperativity [109][110][111] and intramolecular dispersion [112][113][114][115] in various aspects of chemistry is becoming increasingly clear. To date, no SAPT variant which is able to treat systems consisting of more than three fragments has been proposed and other perturbation based many-fragment approaches are also scarce (the efficient, but approximate XSAPT, 116 the Chemical Hamiltonian approach of Halász et al 117 and expensive, highly basis-set dependent supermolecular Møller-Plesset PT methods 118 are noteworthy, but scarcely applied, examples).…”

Controlling supramolecular polymerization through multicomponent self‐assembly

“…[4][5][6][7][8] Many exciting applications have emerged for supramolecular polymers and supramolecular materials, [9][10][11][12][13] that incorporate mechanical, 14 biological, [15][16][17][18][19] optical, 20 or electronic functionalities. 21,22 Similar to covalent polymers, mechanistic investigations of supramolecular systems have highlighted the need to differentiate between the thermodynamically controlled cooperative nucleation-elongation mechanism, noncooperative isodesmic self-assembly or ringchain equilibria, 8,[23][24][25][26][27][28][29][30] and kinetically controlled self-assembly pathways. 22,[30][31][32][33][34][35][36][37][38][39][40][41][42] However, despite the large advances in elucidating mechanistic details, strategies to rationally manipulate mechanisms and self-assembly pathways in supramolecular polymerization remain scarce.…”