Influence of Odd and Even Alkyl Chains on Supramolecular Nanoarchitecture via Self-Assembly of Tetraphenylethylene-Based AIEgens

Salimimarand, Mina; La, Duong Duc; Bhosale, Sidhanath V.; Jones, Lathe A.; Bhosale, Sheshanath V.

doi:10.3390/app7111119

Cited by 8 publications

(7 citation statements)

References 34 publications

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“…The new emission band of axle A1 and [2]rotaxane P1 at λ max 485 nm reached its maximum, as f w increased to 80%, with a remarkable blue shift of ∼15 nm (see Figures and S6, Supporting Information), whereas the fluorescence intensity of [2]rotaxanes P2 , P1-b , and P2-b exhibited supreme bright fluorescence enhancement, as the f w reached 90%, which also showed a significant blue shift of ∼15 nm. The strong fluorescence enhancement of all these TPE–pyrene-containing molecules became fainted with further increment of water contents; therefore, as f w reached 99% in THF/water mixture, untainted aqueous media allowed to form enormous nanoaggregates, which eventually suppressed their emissive decay pathways . To confirm the aggregation capabilities of these TPE–pyrene-containing molecules, we further inspected the fluorescence properties of precursor Py-U in THF/water mixture with various f w .…”

Section: Resultsmentioning

confidence: 92%

“…The strong fluorescence enhancement of all these TPE−pyrene-containing molecules became fainted with further increment of water contents; therefore, as f w reached 99% in THF/water mixture, untainted aqueous media allowed to form enormous nanoaggregates, which eventually suppressed their emissive decay pathways. 48 To confirm the aggregation capabilities of these TPE−pyrene-containing molecules, we further inspected the fluorescence properties of precursor Py-U in THF/water mixture with various f w . The fluorescence intensity of Py-U at λ max 390 and 415 nm progressively decreased with increments of f w in THF/water mixture; however, AIE fluorescence at λ max 485 nm was still not detectable throughout the various f w (see Figure S7, Supporting Information).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Diversiform Nanostructures Constructed from Tetraphenylethene and Pyrene-Based Acid/Base Controllable Molecular Switching Amphiphilic [2]Rotaxanes with Tunable Aggregation-Induced Static Excimers

Arumugaperumal

Shellaiah

Srinivasadesikan

et al. 2020

ACS Appl. Mater. Interfaces

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Dual-emissive tetraphenylethene (TPE) and pyrene-containing amphiphilic molecules are of great interest because they can be integrated to form stimuli responsive materials with various biological applications. Herein, we report the study of mechanically interlocked molecules (MIMs) with aggregation-induced static excimer emission (AISEE) property through a series of TPE and pyrene-based amphiphilic [2]rotaxanes, where tbutylcalix[4]arene with hydrophobic nature was used as the macrocycle. Evidently, by adorning TPE and pyrene units in [2]rotaxanes P1, P2, P1-b, and P2-b, they display remarkable emission bands in 70% of water fraction (f w ) in tetrahydrofuran (THF)/water mixture, which could be attributed to the restricted intramolecular rotation of phenyl groups, whereas prominent blue-shifted excimer emission of pyrene started to appear as f w reached 80% for P1 and 90% for P1-b, P2, and P2-b, which was ascribed to the favorable π−π stacking and hydrophobic interactions of the pyrene rings that enabled their static excimer formation. The well-defined distinct amphiphilic nanostructures of [2]rotaxanes including hollowspheres, mesoporous nanostructures, spheres, and network linkages can be driven smoothly depending on the molecular structures and their aggregated states in THF/water mixture. These fascinating diversiform nanostructures were mainly controlled by the skillful manner of reversible molecular shuttling of t-butylcalix[4]arene macrocycle and also the interplay of multinoncovalent interactions. To further understand the aggregation capabilities of [2]rotaxanes, the human lung fibroblasts (MRC-5) living cell incubated with either P1, P2, P1-b, or P2-b was studied and monitored by confocal laser scanning microscopy. The AISEE property was achieved at an astonishing level by integrating TPE and pyrene to MIM-based reversible molecular switching [2]rotaxanes; furthermore, distinct nanostructures, especially hollowspheres and mesoporous nanostructures, were observed, which are rarely reported in the literature but are highly desirable for future applications.

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Section: Resultsmentioning

confidence: 92%

Section: ■ Results and Discussionmentioning

confidence: 99%

Diversiform Nanostructures Constructed from Tetraphenylethene and Pyrene-Based Acid/Base Controllable Molecular Switching Amphiphilic [2]Rotaxanes with Tunable Aggregation-Induced Static Excimers

Arumugaperumal

Shellaiah

Srinivasadesikan

et al. 2020

ACS Appl. Mater. Interfaces

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“…The fluorescence intensity of [2]rotaxanes R1 and R2 decreased with a further increase of water fraction to >90% f w in contrast to those of axle T1 , [2]rotaxanes R1-b and R2-b , which showed continuous increase of fluorescence until 99% f w . Such a difference is predicted to derive from the large amount of nano aggregates and self-assembled structures in the solution, which lead to the suppression of the emissive nature of AIEgens owing to strong interaction between TPE and macrocycle . The aggregation induced fluorescence of [2]rotaxane R1 was achieved with lower water fraction compared to that of [2]rotaxane R2 , because the nonradiative decay channels were blocked and the radiative transitions were promoted with the help of interactions between t -butylcalix[4]arene macrocycle and TPE.…”

Section: Resultsmentioning

confidence: 99%

“…Such a difference is predicted to derive from the large amount of nano aggregates and self-assembled structures in the solution, which lead to the suppression of the emissive nature of AIEgens owing to strong interaction between TPE and macrocycle. 66 The aggregation induced fluorescence of [2]rotaxane R1 was achieved with lower water fraction compared to that of [2]rotaxane R2, because the nonradiative decay channels were blocked and the radiative transitions were promoted with the help of interactions between t-butylcalix- (DFT) calculations. Geometric optimization using DFT-B3LYP 67,68 with 6-31G basis set was carried out for all the molecules.…”

Section: ■ Introductionmentioning

confidence: 99%

Distinct Nanostructures and Organogel Driven by Reversible Molecular Switching of a Tetraphenylethene-Involved Calix[4]arene-Based Amphiphilic [2]Rotaxane

et al. 2018

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Aggregation induced emission (AIE) active and acid/base controllable amphiphilic [2]rotaxanes R1 and R2 were successfully constructed with tetraphenylethene (TPE) as a stopper and t-butylcalix[4]arene or calix[4]arene macrocycle as a wheel over the axle component. The AIE effect of [2]rotaxanes R1 and R2 was greatly affected by the molecular shuttling of tbutylcalix[4]arene or calix [4]arene macrocycle, which was triggered by the acid/base strategy. In the case of [2]rotaxane R1, aggregation was achieved in the presence of less amount of water compared with those of [2]rotaxane R2, and the deprotonated [2]rotaxanes R1-b and R2-b, owing to the stronger interaction between the TPE and t-butylcalix[4]arene macrocycle and restricted intramolecular rotation (RIR), thus making it responses in less quantity of water along with highly fluorescent emission. [2]Rotaxane R1-b started to aggregate at 70% water fraction (f w ), while [2]rotaxane R2-b started to aggregate at 75% f w which allowed them to morph into hollow nanospheres, whereas they formed only nanospheres at 99% f w in CH 3 CN/water cosolvent system due to the higher degree of aggregation in aqueous media. To our delight, controllable morphology of self-assembled structures was indeed formed from these [2]rotaxanes. Interestingly, by the interplay of a wide range of multi-self-assembly driving forces, the slack stacking of rotaxane unit forms a hollow on the surface of nanospheres to become hollow nanospheres. Among the four [2]rotaxanes studied here, R1 possessed a narrower HOMO−LUMO band gap compared to those others, as confirmed by computational study. Furthermore, only [2]rotaxane R1 formed organogel in methanol solvent and its reversible gel−sol transition could be achieved by the addition of acid and base. This implies that the formation of dumbbell shape cross-linked 3D network structures were mainly governed by π−π stacking, van der Waals force, and intermolecular H-bonding interactions during the gelation processes.

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“…Finally, it was found that NBDF probe produced some mechanochromic effect. The luminescence properties of compounds able to form strong stacked molecular organization are subject to the molecular packing in the solid state [72,73]. Increase in the crystallite size distribution was expected to produce higher PL intensity because of the stacking of the NBDF moieties hinders non-radiative relaxation pathways.…”

Section: Spectroscopic Behaviormentioning

confidence: 99%

A Novel DR/NIR T-Shaped AIEgen: Synthesis and X-Ray Crystal Structure Study

et al. 2020

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We developed a new benzodifuran derivative as the condensation product between 2,6-diamino -4-(4-nitrophenyl)benzo [1,2-b:4,5-b']difuran-3,7-dicarboxylate and 3-hydroxy-2-naphthaldehyde. The intramolecular hydrogen-bond interactions in the terminal half-salen moieties produce a sterically encumbered highly conjugated main plane and a D-A-D (donor-acceptor-donor) T-shaped structure. The novel AIEgen (aggregation-induced enhanced emission generator) fulfils the requirement of RIR (restriction of intramolecular rotation) molecules. DR/NIR (deep red/near infrared) emission was recorded in solution and in the solid state, with a noteworthy photoluminescence quantum yield recorded on the neat crystals which undergo some mechanochromism. The crystal structure study of the probe from data collected at a synchrotron X-ray source shows a main aromatic plane π-stacked in a columnar arrangement.Crystals 2020, 10, 269 2 of 15 law [20][21][22] the intrinsic low band-gap of such DR/NIR emitters makes them especially vulnerable to the ACQ effect [23] due to higher vibrionic coupling between the ground and excited states. Therefore, most of the AIEgens reported emit blue and green lights. Although they are highly sought after for red OLEDs (Organic Light Emitting Diodes), night-vision devices, secured displays, optical waveguides and in the wide field of bio and chemo-sensing [24][25][26][27][28], there are fewer efficient DR/NIR (deep red/near infrared) materials. Of particular interest are AIE fluorophores with intense emission at DR/NIR region owing to their deep tissue penetration, photo-stability and minimum interference in living systems [25,29,30]. Their applications are closely related to cell imaging and DNA and protein sensing [31][32][33].Novel molecular construction of DR/NIR AIEgens can be achieved with electron donor (D) and electron acceptor (A) blocks connected through π-conjugated frameworks. The most fundamental phenomenon governing the spectroscopic properties is the intramolecular charge transfer (ICT) process from the donor to the acceptor in the excited state [34][35][36]. Intercrossed excited state between the low-lying local exciton (LE) and charge transfer (CT) exciton results from the D-A interaction. Obviously, the molecular geometry is crucial for the process.Benzodifuran derivatives have drawn attention for a wide range of biological and pharmacological applications, including antimicrobial, antiviral, analgesic and antitumor [37][38][39][40] activity. This class of heterocyclic compounds are also employed in dyes industry as pigments and in different fields of optoelectronics and photonics. Due to the excellent semiconducting properties [41,42], benzodifuran scaffolds are used as nonlinear optical materials [43], for dye sensitized solar cells [44] and in organic solar cell and transistors. Finally, as electron-rich building blocks they have a potential in the constructing of photoluminescent materials [45][46][47] Herein, we developed a new benzodifuran derivative from 2,6-diamino-4-(4-nitrophenyl) ...

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Influence of Odd and Even Alkyl Chains on Supramolecular Nanoarchitecture via Self-Assembly of Tetraphenylethylene-Based AIEgens

Cited by 8 publications

References 34 publications

Diversiform Nanostructures Constructed from Tetraphenylethene and Pyrene-Based Acid/Base Controllable Molecular Switching Amphiphilic [2]Rotaxanes with Tunable Aggregation-Induced Static Excimers

Diversiform Nanostructures Constructed from Tetraphenylethene and Pyrene-Based Acid/Base Controllable Molecular Switching Amphiphilic [2]Rotaxanes with Tunable Aggregation-Induced Static Excimers

Distinct Nanostructures and Organogel Driven by Reversible Molecular Switching of a Tetraphenylethene-Involved Calix[4]arene-Based Amphiphilic [2]Rotaxane

A Novel DR/NIR T-Shaped AIEgen: Synthesis and X-Ray Crystal Structure Study

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