A Multiresponsive, Shape‐Persistent, and Elastic Supramolecular Polymer Network Gel Constructed by Orthogonal Self‐Assembly

Yan, Xuzhou; Xu, Duanfu; Chi, Xiaodong; Chen, Jianzhuang; Dong, Shengyi; Ding, Xia; Yu, Yihua; Huang, Feihe

doi:10.1002/adma.201103220

Cited by 668 publications

(339 citation statements)

References 107 publications

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“…3, spectrum D). Above 20.0 mM, the peaks undergo broadening that obscures the well-resolved splitting associated with the free ligand and indicates the formation of high-molecular-weight rhombic aggregates (14,19). Despite these spectral changes in the 1 H NMR, the 31 P { 1 H} NMR spectra of 1 have no significant concentration dependencies, with the exception of some broadening that occurs at high concentrations (SI Appendix, Fig.…”

Section: Resultsmentioning

confidence: 96%

“…S30). DOSY was used to probe the dimensions of the polydispersed supramolecular aggregates (14,19). As the concentration of rhomboid 1 was increased between 10.0 and 90.0 mM, the measured weight average diffusion coefficient decreased from 1.07 × 10 −10 to 5.83 × 10 −12 m 2 ·s −1 (D 10.0 mM /D 90.0 mM ∼ 19; Fig.…”

Section: Resultsmentioning

confidence: 99%

“…For instance, organic precursors with hydrogen bonding interfaces can self-assemble into columnar structures (8), a pioneering example in a field that has steadily grown to include a number of materials (9)(10)(11)(12)(13)(14)(15)(16), which have helped establish supramolecular polymerization as a critical subset of materials science (7,(17)(18)(19)(20).…”

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Supramolecular polymers with tunable topologies via hierarchical coordination-driven self-assembly and hydrogen bonding interfaces

Yan

Pollock

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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A powerful strategy to obtain complex supramolecular materials is the bottom-up construction of noncovalently bound materials by hierarchical self-assembly. This assembly process involves stepwise, uniform increases to the architectural complexity of a substrate, starting from discrete precursors and growing in dimensionality through controlled reactivity to a final product. Herein, two orthogonal processes are exploited: coordination-driven self-assembly and hydrogen bonding. The former relies on the predictable formation of metal-ligand bonds wherein the directionalities of the rigid precursors used determines the structural outcome. The latter uses 2-ureido-4-pyrimidinone interfaces that are structurally robust by virtue of the quadruple hydrogen bonding that can occur between subunits. By combining these two processes into a single system, it is possible to generate hierarchical materials that preserve the attractive tunability associated with discrete supramolecular coordination complexes. For instance, the synthesis of a one-dimensional chain comprising linked metalla-rhomboids is readily adapted to a 2D cross-linked hexagonal network by simply selecting a different metal acceptor precursor as an assembly component. The specific interactions between subunits, in this case platinum(II)-pyridyl bonds and the quadruple H-bonding of ureidopyrimidinone, are unchanged, establishing a unique strategy to obtain supramolecular polymers with marked topological differences with minimal synthetic redesign. In addition, the structural rigidity imposed by the inclusion of the platinum metallacycles serves to minimize the formation of cyclic oligomers, increasing the efficacy of formation and improving the properties of the resultant materials. Furthermore, this study taps the potential of organoplatinum(II) metallacycles in materials science.

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Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 99%

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Supramolecular polymers with tunable topologies via hierarchical coordination-driven self-assembly and hydrogen bonding interfaces

Yan

Pollock

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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115

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“…Supramolecular polymers can be defined as dynamically reversible polymeric arrays (29)(30)(31)(32)(33)(34)(35)(36)(37) that form from the explicit manipulation of noncovalent forces between monomeric units (38)(39)(40)(41)(42)(43). Supramolecular polymer chemistry can readily complement coordination-driven self-assembly, as exemplified by our efforts to design hierarchical supramolecular polymerizations of discrete organoplatinum(II) metallacycles, thus accessing novel supramolecular polymeric materials, such as macroscopic hexagonal supramolecular polymer fibers (44), dendronized organoplatinum(II) metallacyclic polymers (45), and a responsive, cavity-cored supramolecular polymer network metallogel (46).…”

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confidence: 99%

Photoinduced transformations of stiff-stilbene-based discrete metallacycles to metallosupramolecular polymers

Yan

Jiang

Cook

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

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Control over structural transformations in supramolecular entities by external stimuli is critical for the development of adaptable and functional soft materials. Herein, we have designed and synthesized a dipyridyl donor containing a central Z-configured stiff-stilbene unit that self-assembles in the presence of two 180°di-Pt(II) acceptors to produce size-controllable discrete organoplatinum(II) metallacycles with high efficiency by means of the directionalbonding approach. These discrete metallacycles undergo transformation into extended metallosupramolecular polymers upon the conformational switching of the dipyridyl ligand from Z-configured (0°) to E-configured (180°) when photoirradiated. This transformation is accompanied by interesting morphological changes at nanoscopic length scales. The discrete metallacycles aggregate to spherical nanoparticles that evolve into long nanofibers upon polymer formation. These fibers can be reversibly converted to cyclic oligomers by changing the wavelength of irradiation, which reintroduces Z-configured building blocks owing to the reversible nature of stiff-stilbene photoisomerization. The design strategy defined here represents a novel self-assembly pathway to deliver advanced supramolecular assemblies by means of photocontrol.metal coordination | supramolecular coordination complex | photoirradiation | reversibility | dynamic materials N atural systems provide many examples of self-assembled biosupramolecules that respond to external stimuli through conformational changes that ultimately play a role in carrying out their various biological functions. Mimicking this stimuli-responsive behavior in artificial systems is a promising route toward obtaining sophisticated molecular-based architectures with functional and structural tunability (1-3). Using the absorption of photons as a trigger is particularly attractive in that light-induced transformations maintain high spatial and temporal resolution without producing waste products even during multiple reversible switching sequences (4). In materials science, one of the most appealing characteristics of photochromic molecules is the direct conversion of light into mechanical energy based on their photo-reversible structural transformations (5). Among such chromophores, a stiffstilbene moiety (1,1′-biindane) is useful owing to its unique characteristics (6). First, stiff stilbene can adopt either a cis or trans configuration with respect to its central double bond. Second, the high activation barrier between the two isomers (∼43 kcal·mol −1 , corresponding to a half-life of ∼10 9 y at 300 K) makes thermal E/Z isomerization negligible at temperatures of 420 K and lower. Third, the quantum yield for the photoisomerization of either isomer is high (50%). Fourth, the stiff-stilbene core is readily substituted using well-established synthetic methods. Owing to these promising characteristics, Boulatov and coworkers (7) constructed a molecular force probe by integrating the moiety into a stretched polymer to mimic the strain gen...

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“…The fluorescent results showed that the assemblies displayed ratio-metric properties with the changes of aggregation-induced emission and monomer-emission, and fluorescence quenching with addition of Pd 2＋ . Keywords tetraphenylethene; DB24C8; secondary ammonium ion; supramolecular polymer; aggregations-induced emission 将高分子聚合物与超分子化学相结合所形成的超分子聚合物是近年来超分子化学领域的研究热点之一 [8] Wavelength/nm …”

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confidence: 99%

Assembly of Tetraphenylethene Containing Amine and Crown Ether Units and Aggregation-Induced Emission Properties

Bian¹,

Ye²,

Zheng³

et al. 2016

Chin. J. Org. Chem.

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Dibenzo-24-crown-8 (DB24C8) and dibenzylammonium (DBA) are always utilized for the construction of supramolecular assemblies. We reported a new kind supramolecular assembly polymer constructed by M1 which was synthesized from tetraphenylethene (TPE) linked with DB24C8 and DBA through click reaction. The chemical structures of all the compounds were fully characterized by 1 H NMR, 13C NMR, and MS. The 1 H NMR titration showed that the supramolecular assembly was successfully constructed in acidic condition. The fluorescent results showed that the assemblies displayed ratio-metric properties with the changes of aggregation-induced emission and monomer-emission, and fluorescence quenching with addition of Pd 2＋ .

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A Multiresponsive, Shape‐Persistent, and Elastic Supramolecular Polymer Network Gel Constructed by Orthogonal Self‐Assembly

Cited by 668 publications

References 107 publications

Supramolecular polymers with tunable topologies via hierarchical coordination-driven self-assembly and hydrogen bonding interfaces

Supramolecular polymers with tunable topologies via hierarchical coordination-driven self-assembly and hydrogen bonding interfaces

Photoinduced transformations of stiff-stilbene-based discrete metallacycles to metallosupramolecular polymers

Assembly of Tetraphenylethene Containing Amine and Crown Ether Units and Aggregation-Induced Emission Properties

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