Supramolecular Competitive Host–Guest Interaction Induced Reversible Macromolecular Metamorphosis

Abstract

In this work, a rational strategy of competitive host–guest complexation between dioxynaphthalene (Naph) and tetrathiafulvalene (TTF) subunits as guests and cyclophane cyclobis(paraquat‐p‐phenylene) (CBPQT4+) module as host is exploited to modify the macromolecular architecture, so‐called supramolecular metamorphosis, in aqueous media. The architectures of the polymers can be reversibly transformed from a linear diblock copolymer AB to a linear AC block copolymer or from a linear block copolymer to a comb copolymer by redox switching. Interestingly, as TTF‐ and Naph‐based complexes feature different characteristic colors, it offers a great opportunity to directly observe nanoscaled macromolecular metamorphosis of materials with the naked eye.

Effect of Host–Guest Complexation on the Thermoresponsive Behavior of Poly(oligo ethylene glycol acrylate)s Functionalized with Dialkoxynapththalene Guest Side Chains

“…mTetEGA was prepared by acrylation of methoxy tetraethylene glycol, whereas NPA was synthesized following our recently reported procedure, using chloroethoxyethoxyethanol instead of previously reported chloethoxyethanol. [ 22 ] The RAFT copolymerizations were carried out in N , N ‐dimethylacetamide (DMA) using azoisobutyronitrile (AIBN) as initiator at 70 °C in the presence of 2‐(((butylsulfanyl)carbonothioyl) sulfanyl)propanoic acid (PABTC) [ 23 ] as RAFT agent with 2 m total monomer concentration. Full experimental details are included in the Supporting Information.…”

An Orthogonal Dynamic Covalent Polymer Network with Distinctive Topology Transformations for Shape‐ and Molecular Architecture Reconfiguration

“…On a broader basis, topological switching for supramolecular networks has also been extensively investigated. The reversible nature of supramolecular self‐assembly via for instance reversible metal‐organic cages and host‐guest interactions offers rich design opportunities [28–30] . The supramolecular systems are, however, limited to soft gels in order to promote the underlying molecular re‐assembly.…”

“…The reversible nature of supramolecular self-assembly via for instance reversible metal-organic cages and host-guest interactions offers rich design opportunities. [28][29][30] The supramolecular systems are, however, limited to soft gels in order to promote the underlying molecular re-assembly. In contrast to the above examples and other topology transformable networks reported in the literature, [31][32][33] the concept of TIN refers specifically to dynamic covalent networks that can undergo topological isomerization after the networks are synthesized.…”