Stimuli-Responsive Two-Dimensional Supramolecular Polymers Based on Trinuclear Platinum(II) Scaffolds: Reversible Modulation of Photoluminescence, Cavity Size, and Water Permeability

Abstract

Here we report the first two-dimensional (2D) supramolecular polymer, which has varying structure and function arising from the perturbation of noncovalent metal···metal interactions in response to acid–base stimuli. This 2D assembly possesses a positively charged, honeycomb-like nanostructure consisting of trinuclear alkynylplatinum­(II) terpyridine complexes appended with acid-sensitive dimethylamino groups. Upon addition of acids and bases, reversible switching mediated by protonation and deprotonation of dimethylamino and dimethylammonium moieties intrinsically alters the positive charge density of the constituent cationic units, which causes interior cavities to adaptively adjust their size, accompanied by drastic photoluminescence changes. When water molecules pass through the membranes obtained from 2D supramolecular polymers, the permeating flux can also be tuned by the pH values of the buffer media. This work paves the way toward supramolecularly engineered 2D smart materials with stimuli-responsive properties.

Toward a Two-Dimensional Supramolecular Organic Framework with High Degree of Internal Order via Amphiphilic Modification

“…19 Self-assembly, with decades of development, has been proven to be an alternative, powerful bottom-up method in the fabrication of numerous supramolecular architectures and soft nanomaterials with diverse topology ranging from zero-dimensional (0D), 20 onedimensional (1D), [21][22][23] and three-dimensional (3D), [24][25][26] to the hierarchical self-assembled systems. 27,28 In terms of 2D nanomaterials, self-assembly has also demonstrated its extraordinary utility in the construction of structurally well-defined 2D assemblies based on rationally designed building blocks driven by various noncovalent interactions including host-guest interaction, [29][30][31][32] metal coordination, 4,[33][34][35] hydrogen bonding, 36 π-π stacking, [37][38][39] ionic interaction, 40,41 as well as Pt⋯Pt 42,43 and cation-π interactions. 44 Among these, the cucurbit [8]uril (CB [8])mediated shape-directed assembly has been proven to be a sufficient strategy capable of directing a 2D extension of building blocks, from which monolayer 2D supramolecular organic frameworks (SOFs) have been constructed in solution phase.…”

A magnetic porous organic polymer: catalytic application in the synthesis of hybrid pyridines with indole, triazole and sulfonamide moieties

“…Pyridine scaffolds as the privileged heterocyclic nucleus have been found in many natural products, pharmaceutical active molecules, organic synthesis, supramolecular chemistry, functional materials, agricultural applications, coordination chemistry and catalytic systems. [19][20][21][22][23] These special systems have a vital role in biologically active natural substances such as nicotine, vitamin B6 and oxido-reductive NADP-NADPH coenzymes. 24,25 The irreplaceable properties of pyridine families as HIV protease inhibitor, 26 anticancer, 27 acetylcholinesterase inhibitor, 24 anti-inammatory, 28 antihypertensive 29 and antidepressant 30 can be a persuasive reason for the synthesis of a new series of these compounds.…”

Hierarchical self-assembly of discrete bis-[2]pseudorotaxane metallacycle with bis-pillar[5]arene via host–guest interactions and their redox-responsive behaviors

“…The discrete metallacycles or metallacages were used either as metallacycle skeletons or stimulus response sites in these supramolecular polymers as reported by various research groups. [10][11][12][13][14][15][16][17][18][19] Such metallosupramolecular architectures are of particular interest not only for their fascinating structures but also because of their stimuli-sensitivities to a wide variety of environmental conditions including solvent composition, pH, temperature, light irradiation, and so on. 20,21 However, the metallacycle-based redox-responsive supramolecular polymers are still rare.…”