Light‐Harvesting Fluorescent Supramolecular Block Copolymers Based on Cyanostilbene Derivatives and Cucurbit[8]urils in Aqueous Solution

Kim, Hyeongju; Nandajan, Paramjyothi C.; Gierschner, Johannes; Park, Soo Young

doi:10.1002/adfm.201705141

Cited by 80 publications

(63 citation statements)

References 70 publications

(82 reference statements)

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“…Aiming at the biosensor application,w eh ave recently synthesized water-soluble version of this AIEEt ype cyanostilbened erivative 2 containing cationic 1-methylpyridinium moiety for hydrophilicity (Scheme 1a). [24,25] As expected, 2 could be dissolved in the pure water but no distinctn anostructure was formed due to the excessive solubility of 2 in it. Therefore, on the basis of the complementary characteristics of 1 exhibitinge xcellent hydrophobic self-assembling propensity and 2 showing high hydrophilicity,w ed esigned in this work an ew cyanostilbene-based amphiphilic molecule, which is (Z)-4-(4-(2-(3',5'-bis(trifluoromethyl)-[1,1'-biphenyl]-4-yl)-1-cyanovinyl)phenyl)-1-methylpyridin-1-iumc hloride (nameda sc yanostilbene 3,S cheme 1a)f or aw ell-structured amphiphilic nanomaterial with bright luminescencei np ure water.I na ddition, to endow cyanostilbene 3 with shape-morphing and fluorescence-switching abilities throughh ost-guesti nteraction (Scheme 1b), [26][27][28][29][30][31] we decided to employ cucurbit [7]uril(CB [7],Scheme 1a)asapartner molecule of cyanostilbene 3.D ue to significant water-solubility and non-toxicity of the CB [7] compared to other macrocyclic hosts, [31][32][33][34] we expected using CB [7] as the partner molecule of cyanostilbene 3 is the best way to achieve the biosensing nanomaterials in pure water.B riefly,w ea ppliedt his shapemorphing nanomaterial consisting of cyanostilbene 3 and CB [7] to af luorescence" turn-on" biological sensort hrough a dynamic competitive guest exchange reaction.…”

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confidence: 63%

Reversible Shape‐Morphing and Fluorescence‐Switching in Supramolecular Nanomaterials Consisting of Amphiphilic Cyanostilbene and Cucurbit[7]uril

Lee

Kim

Park

2019

Chemistry An Asian Journal

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We demonstrate a reversible shape‐morphing with concurrent fluorescence switching in the nanomaterials which are complexed with cucurbit[7]uril (CB[7]) in water. The cyanostilbene derivative alone forms ribbon‐like two‐dimensional (2D) nanocrystals with bright yellow excimeric emission in water (λem=540 nm, ΦF=42 %). Upon CB[7] addition, however, the ribbon‐like 2D nanocrystals immediately transform to spherical nanoparticles with significant fluorescence quenching and blue‐shifting (λem=490 nm, ΦF=1 %) through the supramolecular complexation of the cyanostilbene and CB[7]. Based on this reversible fluorescence switching and shape morphing, we could demonstrate a novel strategy of turn‐on fluorescence sensing of spermine and also monitoring of lysine decarboxylase activity.

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confidence: 63%

Reversible Shape‐Morphing and Fluorescence‐Switching in Supramolecular Nanomaterials Consisting of Amphiphilic Cyanostilbene and Cucurbit[7]uril

Lee

Kim

Park

2019

Chemistry An Asian Journal

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“…As a close analog of azobenzenes, cyanostilbene derivatives have recently been studied for their trans – cis photoisomerization abilities . Interestingly, the cyanostilbene derivatives show 1) strong π‐π stacking interactions to self‐assemble into the supramolecular structures, and 2) bright fluorescence intensities, which characteristically differentiate cyanostilbenes from azobenzenes . In fact, as previously reported, cyanostilbenes are tightly stacking and highly emissive in solid or gel‐like states, while retaining the photoisomerization capability .…”

Section: Introductionmentioning

confidence: 70%

“…Since the self‐assembling supramolecular crosslinkers generating additional supramolecular interactions between the simple molecular crosslinkers should further crosslink and reinforce the polymer gels, we expect that smaller amounts of cyanostilbene crosslinker are sufficient to produce strong and stable photoresponsive polymer gels. Moreover, self‐assembling supramolecular cyanostilbenes should emit enhanced excimeric emission with strong fluorescence intensity in contrast to the weak monomeric emission, based on the aggregation‐induced enhanced emission (AIEE) characteristics of cyanostilbene derivatives . Furthermore, it is rationally expected to show fluorescence photoswitching by the trans – cis photo‐isomerization of the cyanostilbene units.…”

Section: Introductionmentioning

confidence: 99%

A Highly Fluorescent and Photoresponsive Polymer Gel Consisting of Poly(acrylic acid) and Supramolecular Cyanostilbene Crosslinkers

Kim

Lee

Chung

et al. 2018

Advanced Optical Materials

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systems with fluorescence changes is a big challenge for the practical applications such as stimuli-responsive optical memories, detectable drug delivery systems, chemical/biosensors, and bioimaging. [16] In addition, this simple molecular crosslinking strategy using the azobenzene crosslinkers for attaining the polymer gel systems [7][8][9][10][11][12][13][14][15] has not considered the possibility of additional supramolecular interactions between the azobenzene crosslinkers, which can make stronger and more stable gel systems. To address such limitations of the azobenzene crosslinkers in the polymer gels, we aimed at developing a new supramolecular crosslinking agent that can outperform the azobenzene crosslinkers and more importantly generate strong fluorescence in the polymer gels.As a close analog of azobenzenes, cyanostilbene derivatives have recently been studied for their trans-cis photoisomerization abilities. [17][18][19][20][21][22][23][24] Interestingly, the cyanostilbene derivatives show 1) strong π-π stacking interactions to self-assemble into the supramolecular structures, and 2) bright fluorescence intensities, which characteristically differentiate cyanostilbenes from azobenzenes. [25][26][27][28][29][30][31][32][33][34][35][36][37] In fact, as previously reported, cyanostilbenes are tightly stacking and highly emissive in solid [25][26][27][28][29][30] or gel-like states, [31][32][33][34] while retaining the photoisomerization capability. [17][18][19] Since the self-assembling supramolecular crosslinkers generating additional supramolecular interactions between the simple molecular crosslinkers should further crosslink and reinforce the polymer gels, we expect that smaller amounts of cyanostilbene crosslinker are sufficient to produce strong and stable photoresponsive polymer gels. Moreover, self-assembling supramolecular cyanostilbenes should emit enhanced excimeric emission with strong fluorescence intensity in contrast to the weak monomeric emission, based on the aggregationinduced enhanced emission (AIEE) characteristics of cyanostilbene derivatives. [25][26][27][28][29][30][31][32][33][34][35][36] Furthermore, it is rationally expected to show fluorescence photoswitching by the trans-cis photoisomerization of the cyanostilbene units. Upon irradiation of UV light at the well-ordered supramolecular state of trans-cyanostilbenes, trans-to-cis photoisomerization occurs to destroy the supramolecular state of trans-cyanostilbene into the isolated monomeric state. [33] Therefore, based on the unique selfassembling and photoswitchable properties of cyanostilbenes, we herein propose a new strategy using "highly fluorescent A poly(acrylic acid)-based polymer gel exhibiting strong fluorescence and high photoresponsibility is prepared by using a cyanostilbene derivative as a self-assembling supramolecular crosslinking agent, which generates conceptually new multiple hydrogen bonds in the gel system. This polymer gel in ethanol shows the gel-to-sol transition upon UV light irradiation with concomitant f...

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“…Cyanostilbene and its derivatives have been investigated as a novel type of π‐conjugated molecules with “twist elasticity” behaviors according to their inherent molecular structures, which powerfully support the attainment of AIE in the assembled states. In 2018, An and Park, who also discovered the AIE properties of cyanostilbene and its derivatives, reported a new system of supramolecular block copolymers for photosynthesis mimicking ( Figure a) . Four types of cyanostilbene derivatives (represented as B, G, Y, R) were included by CB[8], respectively, via a two‐step process, forming supramolecular homopolymers (SHPs) with a host–guest ratio of 1:1.…”

Section: Aie‐active Supramolecular Nanocomplexes/polymersmentioning

confidence: 99%

“…a) Chemical structures of B, G, Y, and R, b) the photo image of B@CB[8], G@CB[8], Y@CB[8], and R@CB[8] SHPs in water under 365 nm UV light, and c) schematic illustration of the 1:1 cyanostilbene@CB[8] SHP nanobundle in aqueous solution and the stacking mode of the cyanostilbenes. Adapted with permission . Copyright 2018, Wiley‐VCH.…”

Section: Aie‐active Supramolecular Nanocomplexes/polymersmentioning

confidence: 99%

Manipulating Aggregation‐Induced Emission with Supramolecular Macrocycles

Lou

Yang

2018

Advanced Optical Materials

108

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host and guest bears excellent selectivity. [5] On the other hand, the noncovalent interactions are sensitive to various influential elements in the surrounding environment, including light irradiation, [6] redox reactions, [7] pH variations, [8] competitive factors, [9] and chemical or biological interfering. [10,11] Owing to the highly desired characteristics of host-guest systems comprising of supramolecular macrocycles and their guests, the dynamic nature of their molecular activities, the reversibility between assembly and disassembly, the particular intermolecular recognition and the responsiveness toward external stimuli, supramolecular host-guest systems become outstanding candidates as building blocks in the construction of nanoscaled smart materials with controllable properties, which are substantial in the research ranges of nanotechnology and materials science. Up till today, a number of host compounds, such as crown ethers, [12,13] cyclodextrins (CDs), [14] calixarenes, [15] cucurbit[n]urils (CB[n]s), [16][17][18] and pillararenes, [19,20] on account of their developed synthetic procedures, relatively high yieldings, numerous modification possibilities and tunability, [21,22] along with their well-explored host-guest properties, [5] have been utilized to construct stimuliresponsive smart materials to serve as either supramolecular recognizing agents or the major building blocks for reversible artificial complexes. [1,23,24] An important use of macrocyclic compounds to create functional smart materials lies in the construction of controllable fluorescent systems. [25] In the literature, one can find considerable examples of fluorescent systems manipulated by supramolecular macrocycles through their distinctive inclusion complexation activities. [26][27][28][29] The concept of aggregation-induced emission (AIE) was first proposed by Tang and co-workers in 2001, [30] demonstrating an unprecedented fluorescent phenomenon, which bears luminescent features in sharp contrast to the traditional aggregation-caused quenching (ACQ) that is typical for conventional organic fluorophores. While the ACQ effect stands as a major hindrance for the solidation of luminescent materials since luminophores with planar molecular structures undergo fluorescence quenching in aggregated state, dye molecules possessing unplanar conformations, on the contrary, are able to exhibit stronger emission upon aggregation according to the restriction of intramolecular motions (RIM) or rotations (RIR), which suppresses nonradiative relaxation and actuates the energy release through radiative pathway. [31,32] Two essential elements of smart materials are their capabilities of responding to external stimuli and the specific recognition toward different targets, which renders supramolecular macrocycles an ideal type of building blocks for materials construction. Aggregation-induced emission (AIE) has been intensively investigated for two decades not only for the realization of solid-state fluorescent materials, but also for the fabrication...

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Light‐Harvesting Fluorescent Supramolecular Block Copolymers Based on Cyanostilbene Derivatives and Cucurbit[8]urils in Aqueous Solution

Cited by 80 publications

References 70 publications

Reversible Shape‐Morphing and Fluorescence‐Switching in Supramolecular Nanomaterials Consisting of Amphiphilic Cyanostilbene and Cucurbit[7]uril

Reversible Shape‐Morphing and Fluorescence‐Switching in Supramolecular Nanomaterials Consisting of Amphiphilic Cyanostilbene and Cucurbit[7]uril

A Highly Fluorescent and Photoresponsive Polymer Gel Consisting of Poly(acrylic acid) and Supramolecular Cyanostilbene Crosslinkers

Manipulating Aggregation‐Induced Emission with Supramolecular Macrocycles

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