AIEEgens: Recent Advances and


Nov 24, 2017 - It also includes a few mechanistic studies on the structure–property correlation of NIs and provides more insights into the condensed...
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Functional 1,8-Naphthalimide AIE/AIEEgens: Recent Advances and Prospects Peddaboodi Gopikrishna,†,‡ Niranjan Meher,†,§ and Parameswar Krishnan Iyer*,‡,§ ‡

Centre for Nanotechnology and §Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati 781039, India ABSTRACT: This comprehensive review surveys the up-to-date development of aggregation-induced emission/aggregation-induced emission enhancement (AIE/AIEE) active naphthalimide (NI)-based smart materials with potential for wide and realworld applications and that serves as a highly versatile building block with tunable absorption and emission in the complete visible region. The review article commences with a precise description of the importance of NI moiety and its several restricted area of applications owing to its aggregation caused quenching (ACQ) properties, followed by the discovery and importance of AIE/AIEE-active NIs. The introduction section tracked an overview of the state of the art in NI luminogens in multiple applications. It also includes a few mechanistic studies on the structure−property correlation of NIs and provides more insights into the condensed-state photophysical properties of small aggregation-prone systems. The review aims to ultimately accomplish current and forthcoming views comprising the use of the NIs for the detection of biologically active molecules, such as amino acids and proteins, recognition of toxic analytes, fabrication of light emitting diodes, and their potential in therapeutics and diagnostics. KEYWORDS: naphthalimide, aggregation-induced emission, nanoparticles, bio- and chemosensing, drug delivery, cell imaging, OLEDs

1. INTRODUCTION Naphthalimide (NI) core is considered as one of the most versatile fluorophore unit owing to its unique photophysical properties that has been explored extensively in various realworld applications.1 The aromatic core along with the N-imide site can be modified through easy and cost-effective synthetic route that allows for varieties of structural units and functional groups to be fused. As the NI core is electron acceptor in nature, the aromatic core can be functionalized with donor moieties like amine or hydroxyl groups to have a red-shifted intramolecular charge transfer (ICT) band with marked solvatochromic effect. Its UV−visible absorption and fluorescence emission energy falls within the visible region and can be tuned up to near-IR region which could provide an excellent platform to probe the microenvironment of biological systems. Besides, the NI dyes have been used in the construction of novel therapeutics and in the dye industry as a powerful absorber for colorful dyes.2 The NIs and its derivatives have immense potential in the area of optoelectronic materials, fluorescent sensors, laser dyes, bioimaging, etc., because of their extraordinary thermal and chemical stability with high fluorescence quantum yields.1,3 The NIs are also known to have high antitumor activity toward various murine and human cells.4 Again, extension of the aromatic ring with thiazole and polythiazole groups have been manipulated in the construction of several photonucleases and anticancer bleomycin related antibiotics.5 Sulfonated NI derivatives were also reported to have antiviral activity with selective in vitro activity toward the human immunodeficiency virus (HIV-1).6 Brominated NIs at the third and fourth place could act as the photochemotherapeutic © XXXX American Chemical Society

Figure 1. Graphical representation of ACQ NI and AIE/AIEE active NI in solution and aggregated state.

inhibitory materials in blood.7 NI derivatives are also powerful photoreagents and can be photoactivated to kill tumor cells.8 This unlocks their wide probable applications toward phototherapy. The NI core could also be extended for anticancer agents and DNA-binding motifs. In the development of versatile fluorescent materials, a notorious photophysical phenomenon called ACQ frequently comes into the fore and restricts their potential use.9 In solid Special Issue: AIE Materials Received: September 23, 2017 Accepted: November 24, 2017 Published: November 24, 2017 A

DOI: 10.1021/acsami.7b14473 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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ACS Applied Materials & Interfaces state or in poor solvent, fluorescent properties of the classical fluorophores are destroyed through the formation of

Figure 2. Possible technological applications of the AIE/AIEE active NIs.

aggregates. Most of the conventional organic fluorophores exhibited planar structures that have strong affinity to pack closely in their condensed state through intermolecular π−π interactions. Because of the strong packing, these fluorophores relax via nonradiative pathways and the emission quenches effectively. This is mainly due to the H-type aggregation of the fluorophores and thus the phenomenon is termed as ACQ. However, in the solution state, the fluorophores remain in the molecularly dispersed state and display high fluorescence emission due to lack of aggregation. The ACQ effect has restricted many real-world technological applications, because, practically a fluorophore is frequently used as a whole (aggregate), rather than in its monomeric form. Also, considering the practical applications, the sensory materials (chemoor biosensors) ought to work in physiological conditions. Although polar functional moieties like carboxylic and sulfonic acid groups can be integrated with the hydrophobic aromatic cores, the subsequent fluorophores still display aggregation behavior in water owing to the high hydrophobicity of the aromatic cores and the alkyl chains through which they are

Figure 3. Representation of NI core indicating the most reactive positions (red star).

Figure 4. Classified model structures of NIs based on their bond connectivity.

Scheme 1. Possible Synthetic Routes for Producing the AIE/AIEE Active NIs

B

DOI: 10.1021/acsami.7b14473 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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and experimental proof, restriction of intramolecular motions was hypothesized to be the most reliable and effective working mechanism for their condensed state emission. Applying fundamental physics to the organic molecules having rigid rotators, upon excitation, could consume maximum amount of energy through dynamic intramolecular rotation and vibrations. Because of this, they became less emissive or nonemissive in solution state. Whereas, in aggregated or solid state, the molecules interlock themselves that restrict the intramolecular rotation (RIR) and vibration and relax through radiative pathways. It is also noteworthy to mention that the molecules should not acquire a dense face-to-face packing that favors the strong π−π stacking interaction and subsequently the radiationless relaxations and bothachromic shifts, often seen in the crystals of the conventional luminophores or ACQphores. Considering these prospects, the well-known AIEgens (TPE, HPS, etc.) were designed in such a way that their propeller shaped molecular conformations restrict intermolecular π−π stacking interaction and make them highly emissive in their condensed state. This general concept can be applied to any planar ACQ system to induce AIE properties through structural manipulation (by disturbing their planarity, which will prevent the dense faceto-face packing). To date, a wide variety of cores with the AIE or AIEE properties have been reported. They include tetraphenylethenes (TPE), siloles, diphenyldibenzofulvenes, anthracene derivatives, pyrrole, cyanostilbenes, phenothiazine derivatives

usually functionalized. The ACQ effect has a huge adverse impact on the fabrication organic light-emitting diodes (OLEDs) devices, where the active materials are generally applied in the aggregate state as thin films. These observations indicate that ACQ is a negative optical effect preventing their wide and versatile application as light emitting materials. Tang et al. in 2001 discovered an interesting phenomenon based on propeller shaped silole derivatives which were found to have exactly opposite photophysical properties to that of ACQ properties and this phenomena was termed as aggregation induced emission (AIE).10 These luminogens are highly fluorescent in condensed state but they became nonemissive in solution state. Following the discovery, Park et al. in 2002 introduced another phenomenon called as aggregation induced emission enhancement (AIEE), a subgroup of AIE.11 AIEEactive molecules exhibit emission in all physical states like solution, solid and aggregated state. To get into the mechanistic insight of this interesting phenomenon, many research groups hypothesized several mechanistic pathways including J-aggregate formation, conformational planarization, twisted intramolecular charge transfer (TICT), excited state intramolecular proton transfer (ESIPT) and E/Z isomerization.12 However, none of these mechanisms could be universalized because of their inapplicability to all the reported AIE and AIEE systems. In 2015, Tang and co-workers once again tried to generalize its working mechanism and drew a strong aspect regarding the AIE/AIEE process.9 In that review article, with solid theoretical

Figure 5. Possible mechanisms of AIE/AIEE of 1a, 1b, 1c, and 1d with casein. Reproduced with permission from ref 17 and18. Copyright 2013 Elsevier.

Figure 6. Chemical structure of 2; suggested mechanisms for AIEE and TICT processes and DFT optimized structures of protonated compound 2 (DONH+) with electron distribution in HOMO and LUMO. Reproduced with permission from ref 19. Copyright 2012 Elsevier. C

DOI: 10.1021/acsami.7b14473 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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derivatives. The discussion part is tracked by an overview of the up to date report of NI AIE/AIEEgens. The instances summarized herein are mainly grouped according to the bond

and diketopyrrolo-pyrrole derivatives, ESIPT molecules, phosphole and organoborons, o-carborane dyes, phosphindole oxides, pyrazine derivatives, metal complexes, NIs, etc.9,12,13 In the past decades, although N-imide-functionalized NI probes have been widely used as a classical fluorophores, their ACQ properties screen their potential applications. To the best of our knowledge, in 2011 Chang and co-workers reported AIEEactive NIs for the first time by extending the π-conjugation by core substitution with rigid aromatic units.14 These V-shaped nonplanar and flexible NIs were reported to form fluorescent organic nanoparticles with AIEE characteristics. As shown in Figure 1, the highly fluorescent planar NI molecules (in solution state) were extensively affected by dense face-to-face packing and got quenched in the aggregated state through H-aggregation. However, their core substitution with rigid aromatic core restricts their H-type aggregation (nonfluorescent or weakly fluorescent in solution state because of dynamic rotation and vibration), and became highly fluorescent in aggregated and solid state (Figure 1). This example established that an ACQ fluorophore can be easily transformed into an AIE-active material by breaking its planarity through rigid aromatic core substitution. There are also some other methods, such as appending ACQ units on a polymeric chain to synthesize AIEgens. The basic aim of such structural transformation is to restrict the molecules to form H-aggregates through π−π stacking in poor solvent or solid state. Subsequently, this ACQ hurdle was potentially resolved by well-designed structural modifications by various research groups. To date, the number of NI derivatives have been reported with high fluorescence quantum yields in solid or aggregated state by introducing different organic moieties at fourth position or by N-functionalization, and opened up various restricted areas with potential applications (Figure 2). These transformed luminogens could be efficiently employed in OLEDs along with brightening material to stain living cells. Most of the luminogens are usually insoluble in aqueous media yet can form highly stable fluorescent organic nanoparticles. These nanoparticles with higher surface area along with their inherent molecular properties can be used for various biological activities both in vitro and in vivo. Thus, it is evident that the NI derivatives have found wide applications, in the past few years and many outstanding examples of NI based AIE/ AIEEgens have been reported, that demonstrate the high versatility of this NI core by integrating them with the young concept of AIE/AIEE. Because of the easy N-functionalization of the 1,8-naphthalic anhydride precursor with simple Gabriel phthalimide synthesis, most literature has reported substituting the nonpolar alkyl groups to form imide linkages that enhanced the solubility in organic solvents. Apart from this, some other reactive positions are available on naphthalene moiety, as shown in the Figure 3, which could be easily functionalized by rigid aromatic core to transform the ACQ fluorophore into AIE/AIEEgens. In particular, the fourth position has been manipulated in most of the examples because of their easy and cost-effective synthetic route. The various facile synthetic routes that have evolved in past decades are summarized in Scheme 1. This review concentrates on the importance and versatility of NI core integrated with AIE properties for the development of various smart materials; beginning with a short introduction on the significance of the NI core, a discussion on the hurdles for their wide application as a result of ACQ phenomenon, followed by the introduction and mechanism of AIE in NI

Figure 7. Chemical structure of 3 and probable aggregation arrangement of molecules with different alkyl chain length. Reproduced with permission from ref 20. Copyright 2013 American Chemical Society.

Figure 8. Graphical representation of the synthesis of 4 FONs and the strategy for Fe3+ detection and imaging. Reproduced with permission from ref 21. Copyright 2014 The Royal Society of Chemistry.

Figure 9. (a) The chemical structure of 5 and (b) the single-crystal structure of 5. (c) Sketch of the probable thermochromism and vapochromism mechanisms of 5. Reproduced with permission from ref 22. Copyright 2014 The Royal Society of Chemistry.

Figure 10. (a) Chemical structure, (b) single-crystal structure, (c) structural arrangement showing ππ interactions, (d) fluorescence image of 6 crystals under 365 nm UV illumination. Reproduced with permission from ref 22. Copyright 2014 The Royal Society of Chemistry. D

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2. NIS WITH N-FUNCTIONALIZATION (I) Four NI-based (1a, 1b, 1c, and 1d) water-soluble fluorophores with carboxylic groups were developed by Sun and co-workers and were successfully utilized for turn-on sensor of casein through the AIE phenomenon.15−18 These NIs were applied for its quantification in milk powder samples. The molecules possess donor and acceptor units that can modulate its photophysical properties by varying solvent polarity. Self-association and TICT played a significant role that caused to decrease the fluorescence intensity in solution state. These molecules bind efficiently with Tyrosine and Tryptophan residues present in the hydrophobic cavity of casein that were consequently responsible for the aggregation of molecules on the casein surface with enhanced emission. Accordingly, a novel casein assay method was developed with a detection limit of 5.6 ng/mL for the water-soluble NI fluorophore 1a. The highly reversible and reproducible result achieved from this method was found to be in good agreement with the Biuret technique result for casein quantification in milk powder. However, the NI fluorophores with a single electron-donating group affected the binding of 1a with casein because of the inhibition of PET in the presence of transition metal ions Fe3+ or Cu2+ and showed high fluorescence enhancement. The sensitivity and selectivity was improved for 1b, 1c, and 1d fluorophores, which were developed by changing the core substitution at fourth position. The sensitivity was increased up to a limit of detection of 2 ng/mL, (LOD for 1a, 5.6 ng/mL; 1b, 3.0 ng/mL; 1c, 2.8 ng/mL) but the interference of transition metal ions like Fe3+ and/or Cu2+ remained as a drawback for these AIEgen systems. The highest sensitivity was achieved with fluorophore 1d because of the presence of four carboxylic acid groups which were bound to casein more compactly and became more hydrophobic (Figure 5). Between casein and fluorophores, a new complex formation was

connectivity to the NI core (Figure 4), which mainly involved the N-functionalization and the fourth position substitutions.

Figure 11. Chemical structures of 7 and 8. Schematic diagram showing solubility trends versus aggregation behavior. Reproduced with permission from ref 23. Copyright 2014 The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.

Figure 12. Representative energy diagram for NI derivatives in (a) highly nonpolar and (b) highly polar solvents. Reproduced with permission from ref 23. Copyright 2014 The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.

Figure 13. (a) Emission spectra of 7 with 15 μM concentration (at different f w), and (c) 25 μM concentration of 7 in H2O−CH3CN. λex = 334 nm. Inset: photographs of vials under 365 nm UV illumination, and (c) fluorescence spectra of 8 in CH3CN solutions having f w in the range of 0−70%. (b, d) Fluorescence quantum yields of 7 and 8 in CH3CN solutions at different f w in the range of 0−95%. Reproduced with permission from ref 23. Copyright 2014 The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC. E

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Figure 15. Confocal fluorescence microscopy photographs of HeLa cells incubated with (a, b) P2, (e, f) P3, and (i, j) P4-based nanosensors and (c, g, k) Lyso Tracker Deep Red. The fluorescence images in the first, second, and third columns were obtained in the blue channel (430−490 nm, λex = 405 nm), green channel (500−550 nm, λex = 405 nm), and red channel (650−700 nm, λex = 635 nm). (d, h, l) Merged images of blue, green, and red channels. Reproduced with permission from ref 24. Copyright 2015 American Chemical Society.

Figure 14. Chemical structure of 9 and 10. Representation of hyperbranched polylactide polymers. (a) Normalized PL spectra of P1−P5 in K2HPO4/KH2PO4 buffer solutions (pH 7.0), (b) fluorescence images of P1−P5 observed under 365 nm UV illumination, (c, d) SEM images of P2, P3 polymer nanoparticles, (e) normalized (I450 nm) PL spectra of P3 (20 μg mL−1) in 0.1 M K2HPO4/KH2PO4 buffer at various pH, (f) study of pH reversibility of P3 between pH 5.0 and 8.1. λex = 365 nm. Reproduced with permission from ref 24. Copyright 2015 American Chemical Society.

Figure 16. (Left) Chemical structures of luminogens (11, 12, 13, 14) and (a−c) TEM images of 11 nanoaggregates. Inset in panel c shows the compact morphology of the nanoring. Black circle in panel a indicates the plausible spherical stricture of the nanoaggregates. The yellow circles in panels a and b show the existence of (d) a tiny ringlike nanoaggregate, which is schematically presented in d. Reproduced with permission from ref 25. Copyright 2015 American Chemical Society.

responsible for the AIE phenomenon, which reduced the solubility in water. NIs based simple donor−acceptor (Figure 6) AIEE luminogen 2 with positive solvatochromism was reported and applied for proton sensor by Yang et al.19 The absorption and emission wavelengths were red-shifted and the emission intensities were reduced from nonpolar to polar solvents. The fluorescence spectra were recorded under different pH conditions and a gradual increase in the blue-shifted emission intensity was observed by changing the pH range from 7.6 to 5.0. This was mainly due to the protonation on the imide moiety that restricted the photoinduced electron transfer (PET) in the molecules and served as a proton sensor. Sarkar et al. reported a series of 4-bromonaphthalimide (3-Cn) congeners with different alkyl side chains (3-Cn; n = 4, 6, 10, 12, and 16) to fabricate organic fluorescent micro materials (Figure 7).20 In this study, the effect of alkyl chains that played the character analogous to that of stabilizing additives on the aggregation behavior was investigated by spectroscopic and microscopic techniques. To investigate the

AIE phenomenon, they performed fluorescence study for 3-C12 by changing water fraction ( f w) in DMSO, clearly indicating that the emission intensity gradually increased up to 70% on increasing the f w because of the formation of nanoaggregates (which were confirmed by FESEM and DLS studies). A further increase in the f w caused a decrease in the fluorescence intensity because of the formation of agglomeration. Microscopic investigation exposed the decline in the aggregates size with an increase in the length of alkyl side chain. The microscopic investigation revealed that with increasing length of the alkyl chain the nanoaggregate shapes changed from rod-like to spherical. It was concluded that the alkyl chain length dependent aggregation properties could be due to the interplay between the intermolecular forces. The photophysical properties clearly F

DOI: 10.1021/acsami.7b14473 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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Figure 17. (A) & (B) Mechanism of circular aggregation formation of 11. Reproduced with permission from ref 25. Copyright 2015 American Chemical Society.

Figure 18. Chemical structures of 15 and 16 and optical (insets) and negatively stained TEM images of hydrogels for (a) 15 and (b) 16 at a concentration of 1 wt % at pH 7.0 (the scale bar is 100 nm). Reproduced with permission from ref 26. Copyright 2016 American Chemical Society.

Figure 19. Concentration pH phase diagrams for (a) 15 and (b) 16 (S, solution; G, gel; and P, phase separation) and PL spectra (λex, 340 nm) of (c) 15 and (e) 16 at 500 μM at pH 7.0 in DMSO solutions with different f w. Relative emission intensity (I/I0) plotted with respect to the f w in DMSO for (d) 15 and (f) 16. I0: fluorescence intensity of 15 or 16 in pure DMSO. Reproduced with permission from ref 26. Copyright 2016 American Chemical Society.

indicated that the emission and absorption spectra were redshifted for all fluorophores from molecular forms to aggregates owing to the J-aggregates formation. A confocal fluorescence microscopic examination was also conducted and the long chain systems were found to have the cell permeability that could be applicable in live cells imaging.

Xu et al. reported (Figure 8) highly sensitive and selective “turn-on” fluorescent probe to detect Fe3+ in aqueous media based on novel NI-diethylenetriamine-quinoline (4) derivative.21 The AIEE activity of the probe was analyzed in acetonitrile and water mixtures where 4 formed fluorescent nanoparticles in water, which were confirmed by the TEM analysis. G

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Figure 20. Chemical structures of luminogens (17, 18, 19, and 20).

Figure 21. π···π interaction diagrams of (a) 17, (b) 18, and (c) 19 showing distances between tricyclic core. Reproduced with permission from ref 27. Copyright 2016 American Chemical Society.

Figure 23. Chemical structures of 22, 23, 24. Fluorescence images 22 in different solvents, from left to right in blank, toluene, cyclohexane, hexane, CHCl3, CH2Cl2, ethyl acetate, THF, acetone, acetonitrile, DMSO, DMF, and ethanol. λex = 390 nm. (a) PL spectra of 22 in THF-H2O systems ( f w = 0−90%). Inset: plot of PL intensity at 570 nm and λem,max changes with f w. (b) PL spectra of 23 in THF-H2O mixtures with f w varying from 0 to 100%. Inset in (b) are photographs of the polymer solutions in THF-H2O mixtures. Reproduced with permission from ref 29. Copyright 2017 The Royal Society of Chemistry.

disappear with heating or exposing to CH2Cl2 and CHCl3 vapors. This resulted in the transition of the crystal packing from J-type aggregation to H-type excimer formation, similar to the crystal packing of 6 (Figure 10). Again, the molecular packing transition was reversible that makes the simple NIs potentially effective candidates to develop stimuli-responsive fluorescent materials. Cho and co-workers investigated the effect of solvent polarity on the nature of aggregation. They reported two NI AIEgens to describe the reason for AIE phenomenon in different types of NI derivatives (7 and 8).23 The chemical structures of luminogens are shown in Figure 11. Theoretical calculation suggested the lowering of T2 state compared to the S1 state in nonpolar solvents that facilitated the intersystem crossing, whereas the emission intensity got increased by increasing the solvent polarity (or Protic polar solvent fraction like water) and could be attributed to the S1 and T2 states of energy ordering (Figure 12). As shown in Figure 13 the luminogen 7 showed red-shifted AIE in highly polar or nonpolar solvents and can be correlated with the formation of excimer through intermolecular π−π interaction. However, in the case of 8, with D−A combination, AIE could be due to intramolecular charge transfer complex (exciplex) formation. Smet et al. reported for the first time an AIE-active hyperbranched polymer nanoparticle (Figure 14).24 The NI based AIE polymer nanoparticles were ratiometrically utilized for intracellular pH sensor. These polymers showed excellent

Figure 22. Chemical structure of 21 and TEM image of 21 nanoparticles. Reproduced with permission from ref 28. Copyright 2016 The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.

These nanoparticles were successfully utilized for the imaging studies of the Fe3+ in the living cells. The nanoparticles exhibited super optical properties with excellent biocompatibility and could endorse a possible convenient assay for disease-related studies. In this study, Liu et al. demonstrated an easy synthetic and structurally simple NI luminogen with intense blue emission.22 The novel NI (5) displayed significant luminescence vapochromic and thermochromic characteristic owing to the interconversion in the dynamic self-assembly from J-type aggregate to H-type excimer state (Figure 9). The absolute quantum yield of 5 exhibited 82.33% in solid state. Through a comparative study, the prime role of bromine atom in the molecular self-assembly was confirmed through the single crystal analysis. The strong blue emission could be due to J-type aggregation as confirmed from the single crystal analysis. However, it was assumed that the poor intermolecular C−H···O hydrogen bonding could H

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Figure 24. Structure of compounds 25 and 26. (a) Packing diagram of 25 showing H-bonds. (b) Interplanar angle between the amide and pyridyl plane. Reproduced with permission from ref 30. Copyright 2017 Elsevier.

Figure 25. PL spectra of (a) 25 and (b) 26 as pristine, ground and annealed solids (λex = 340 nm) and images were obtained under 365 nm UV irradiation. Reproduced with permission from ref 30. Copyright 2017 Elsevier.

along with the role of individual 9 and 10 monomers, five polymers (P1−P5) were synthesized by varying the ratio (the molar seed ratios of 9 and 10 are 1:0, 3.3:1, 1:1, 1:2.5, and 0:1 for P1−P5, respectively) of 9 and 10. Among all polymers, the P1 polymer exhibited the AIE activity efficiently. In addition, polymer P6 was also synthesized for the comparison without using any 9 and 10 units, which showed strong fluorescence in DMF but gets quenched in water. The polymer nanoparticles were prepared by the nanoprecipitation method. The polymers showed ratiometric color change with pH. The pH responsive polymers were studied by the PL spectra (Figure 14a) at different pH ranges from 4.7 to 8.0. Among all the polymers, P3 demonstrated huge tuning of emission color from blue (∼450 nm) to green (∼520 nm) while moving from pH 8.1 to 5, respectively. The pH response is due to the intramolecular PET from the donor to the NI acceptor moiety. The quantitative investigations of intracellular pH in HeLa cells were performed with this ratiometric nanosensor that gave the first example to construct intracellular pH sensor with AIE hyperbranched polymer nanoparticles. Confocal fluorescence microscopy photographs of HeLa cells are given in Figure 15. The effect of core substituted halogens on the selfaggregation behavior of NI derivatives (11, 12, 13, and 14) was explored by Bhattacharya et al.25 These luminogens exhibited the unusual AIEE behavior in aqueous solution. In their work the mechanistic impact of chloro-substitution toward intermolecular electrostatic communication to shape up nanorings via J-type aggregation was emphasized. The J-aggregation formation via in-plane oblique angle conformation was also justified by the angle restriction rule proposed by Kasha. According to Kasha’s rule, J- or H-aggregates can be defined by the angle (φ) between the adsorption surface and the longitudinal axis of the molecules. φ > 54.7° signified the formation of H-aggregates, whereas for φ < 54.7°, J-aggregates are formed. Thus, the angle α and φ was calculated to be 123

Figure 26. Chemical structures of 27, 28 and 29. Changes in solution color of 27 (1 μM) with increasing f w in mixed PBS buffer:DMSO solvents, under 365 nm irradiation. Emission variation of the 27 treated paper strip (a) before and (b) after dipping the strip into a 1 M TNP solution or after introduction of few drops of (c) H2O or different concentrations of a TNP solution: (d) 1 nM, (e) 3 nM, or (f) 10 nM 4 L of water or a TNP solution was supplemented onto the paper strips. The fluorescence emission of the paper strips was noticed under 365 nm illumination. Reproduced with permission from ref 31. Copyright 2017 Elsevier.

biocompatibility and can also be selectively accumulated in acidic organelles of living cells. Before synthesizing the polymers, the AIE activity of the 9 and 10 monomers were examined in different DMF/Water and both the monomers were found to exhibit AIE properties in water with blue and green emissions, respectively. To have a better understanding on the aggregation properties of the hyperbranched polymer I

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Figure 27. Synthesis of 4-(N-methylpiperazine)-1,8-NI-polyisoprene (Napht-PI) conjugated system by NMP and formation of AIEgenic polymer prodrug nanoparticles via its conanoprecipitation with cladribine-diglycolate-polyisoprene (CdAdigly- PI). Reproduced with permission from ref 33. Copyright 2017 The Royal Society of Chemistry.

Figure 28. Evolution of the fluorescence emission at 520 nm (λex = 420 nm) of (a) 31 (10 mM) and (b) P1 at 500 nm and P2 at 490 nm (λex = 420 nm) (10 mM) with the volume fraction of water in THF. Inset: (a) Photographs of the 31 solutions at different f w under U.V (λ = 365 nm) and (b) picture of P2 in THF and in 99% water under U.V. (λ = 365 nm). Reproduced with permission from ref 33. Copyright 2017 The Royal Society of Chemistry. Figure 30. Chemical structures of 39, 40, and 41 and dimeric π−π stacking in the condensed state structures of 39−41 (from left to right). Photographs of the solid powders of 39−41 (from left to right) under ambient (top) and UV (bottom) illumination. Adapted with permission from ref 35. Copyright 2014 Wiley−VCH.

nanorings were analyzed and confirmed by both theoretical and experimental studies. Visual confirmation of the fluorescent organic nanoaggregates (FONs) was done by TEM images (Figure 16) and was found to be of 7.5−9.5 nm. Through several conclusive analyses, it was presumed that the existence of much attractive electrostatic force between the monomer 11 is presumed to be the principal fact directing for the formation of nanorings architecture (Figure 17). Additionally, NI fluorescent organic nanoaggregates (FONs) were also demonstrated as a sensitive and specific probe for cysteine. The precise property of 11 nanoaggregates toward amino acids was also applied in molecular logic gate. Lin et al. reported two tripeptide functionalized NI with significant difference in their supramolecular hydrogelation and chemical structures of NI derivatives (15 and 16) as shown in Figure 18.26 The AIE characteristics of hydrogelators were proved by PL studies using DMSO and water mixtures with 500 μM concentration (Figure 19). In pure DMSO solution both hydrogelators were almost nonemissive, and remain nonemissive up to 60% f w. The fluorescence intensity was gradually increased with increase in the f w from 60 to 99%. They achieved diverse self-assembly properties just by varying

Figure 29. Chemical structures of luminogens (32, 33, 34, 35, 36, 37, and 38) and digital photographs of compounds 32−38 (1−7) under white-light illumination and 254 nm UV illumination (left to right, respectively). Reproduced with permission from ref 34. Copyright 2014 the PCCP Owner Societies.

and 28.5° at concentration 14 μM, whereas it is 131.5 and 24.3° at concentration 48 μM, respectively. The formation of J

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Figure 31. Chemical structures of the 42, 43, and 44 and TEM photographs of aggregates of (a, b) 42, (c, d) 43, and (e, f) 44 in THF/H2O (1:90) (1 × 10−4 M). Adapted with permission from ref 37. Copyright 2014 Wiley−VCH.

was confirmed by the DLS and TEM analysis (Figure 22). The nanoaggregates exhibited good emission with a red-shift of 55 nm from THF solution to water (340 to 395 nm) along with a new peak appearing at ∼500 nm. Fluorescence titration showed that, the ligand could detect as low as 64 nM Cr3+ ions in aqueous media. To elucidate the sensing mechanism of the 21, DFT studies were performed which showed that Cr3+ had the capability to extract electrons from the triethylenetetramine units and inhibited the PET. Zhu et al. designed and synthesized a TPE substituted at 4,6-positions of naphthalimide (22) monomer. This monomer was further utilized for the synthesis of copolymers 23 and 24 and the monomer and copolymers (structures shown in Figure 23) exhibited both ICT and AIE characteristics.29 Monomer and copolymer showed strong solvent-dependent emission properties in various solvents. Test papers were fabricated with the probe to distinguish common organic solvents under UV light. As shown in Figure 23 the test papers of 22 exhibited emission colors in the entire visible region from blue to red and the fluorescence was completely quenched in ethanol according to the diverse solvent properties. More fascinatingly, they could easily discriminate CHCl3 and CH2Cl2 using this fabricated test paper. Figure 23a, b explained the aggregation properties of both 22 and 23 that were studied in THF and water solvent system and observed that both exhibited excellent AIEE characteristics. It was observed that copolymer 23 showed thermoresponsive characteristics and the fluorescence intensity changed with respect to temperature. The fluorescence intensity steadily amplified from 20 to 34 °C because of the thermo-induced shrinking of the 23 chain, whereas it decreased continuously after 34−90 °C, which could be due to the well-known thermal effects. Furthermore, they synthesized water-soluble copolymer 24 by introducing a hydrophilic unit HEA into the copolymer successfully. The copolymer containing a TPE unit, a mitochondria label, was highly soluble in water with high fluorescence quantum yield that was applied as a mitochondria targeted imaging tracker in HeLa cells. Thus, this kind of probe with combined AIE and ICT characteristics could serve as a powerful candidate for multiple applications like mitochondria targeting imaging, solvent, thermosensor, etc. Mishra et al. reported two N-functionalized NI AIEEgens such as 25 and 26 (Figure 24) with reversible mechanochromism (MC) and multistimuli response.30 The AIEE phenomenon carried out using DMF and water mixtures for both compounds and the nanoparticle formation was supported by SEM and TEM analysis in the 4:6 DMF and water. As shown in the Figure 25, both 25 and 26 exhibited MC with indigo light emission at 438 and 428 nm, respectively. After grinding, the

Figure 32. Confocal fluorescence images of HeLa cells with dyads 42 and 43 (1−3) costained with Hoechst 33342. The photographs from left to right displayed staining with the dyad followed by Hoechst 33342 nucleus staining images, bright-field images, and a merged image of the first three images. Adapted with permission from ref 37. Copyright 2014 Wiley−VCH.

the order of the peptide chain. The phase diagrams revealed (Figure 19) that 15 could assemble to a stable gel at pH 7, whereas 16 did not undergo gelation in similar conditions. Computational and spectroscopic investigations suggested that the extended hydrogen bonding along with intermolecular π−π interactions might strengthen the formation of AIE-active fluorescent nanostructures in 15. In addition, the luminogens 15 was found to have good biocompatibility and could be a promising material for biological system. These results basically highlighted the significance of peptide sequences in a selfaggregating hydrogel system. Four new N-functionalized NI derivatives (17, 18, 19 and 20) were synthesized by Mishra and co-workers by varying the functional groups on the phenyl ring (Figure 20).27 They formed fluorescent nanoaggregates in water-DMF solution with AIE phenomenon. The nature of nanoaggregates formation was explained through their single crystal analysis (Figure 21) and SEM analysis. Antiparallel dimeric interactions in the solid state formed a herringbone architecture to 17 and 2D channel and stairlike architectecture for 18 and 19, respectively. The density functional theory (DFT) calculations also supported their intermolecular interaction and cumulative electronic behaviors in these NI derivatives. Kaur and co-workers reported simple symmetric dimer of NI based ligand (21) and prepared their nanoaggregates by simple reprecipitation method.28 These nanoaggregates were found to show excellent sensitivity toward Cr3+ in aqueous media. The uniform nanoaggregates were prepared by the addition of 0.1 mL THF solution of the ligand 21 in 100 mL of water and K

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Figure 33. Chemical structure of 45 and 46. (a) UV−vis spectra of (b) 45 PL spectra (λex = 355 nm) of 45 (1.0 × 10−5 mol L−1 in THF/H2O mixtures) and (c) dihedral angles of the aggregation-induced chiral binaphthyl derivatives. Adapted with permission from ref 39. Copyright 2015 Wiley−VCH.

Figure 34. Chemical structures of 47, 48, 49, along with the corresponding digital photographs at different f w values in DMF under white-light and 365 nm irradiation. (a, b) ORTEP diagram of compound 47 and 48 with the thermal ellipsoids set at 50% probability, respectively. (c) Crystal packing of 47 showing head-to-tail π−π interactions. (d) Crystal packing of 48 showing slipped π−π stacking. (e) Slipped π−π stacking of NI core showing the inclined angle and shortest distance in 48. Reproduced with permission from ref 40. Copyright 2016 The Royal Society of Chemistry.

emission color was red-shifted to super blue emission (469 and 473 nm) and was retained by annealing of the ground samples at 220 °C for 15 min. This MC property was confirmed by crystal structure (Figure 24) and SEM analysis. The powder XRD analysis revealed that before grinding the compounds exhibited the crystalline nature with sharp peaks, and the samples were converted to planar amorphous nature after grinding. These amorphous molecules exhibited the planar structures that are highly favorable for bathochromic shifts in their emission.

Chae et, al. reported two NI-conjugated sulfonamide probes (27 and 28) for the detection of TNP in water.31 The AIEE properties (Figure 26) of the probes were analyzed in DMSO and water mixtures, where the fluorescence intensity of the probes increased with increasing f w in DMSO without any shift in the λmax (∼484 nm). This was due to the formation of fluorescent nanoparticles in water. Among both the AIEE-active probes, 28 showed superior sensitivity toward TNP. Besides, the 27 showed good selectivity toward TNP in the presence of L

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Figure 35. AFM topography images of (a) 47, (b) 48, and (c) 49 formed by the evaporation of the compounds in a 99.9% water-0.1% DMF mixture at room temperature (10 mM). FE-SEM images of (d) 47, (e) 48, and (f)49 prepared by the evaporation of the probes from a 99.9% water-0.1% DMF mixture on aluminum foil at room temperature (10 μM). Reproduced with permission from ref 40. Copyright 2016 The Royal Society of Chemistry.

other competing nitro-explosives. The sensing studies for 27 was performed both in PBS buffer and in the seawater; the observed and calculated detection limits of the 28 were 3 nM and 5.86 ppt, respectively. Furthermore, they also performed the solid state sensing of the TNP using probe-loaded paper strips that provided an effective and appropriate tool for onsite detection. The same group also reported N-functionalized AIEE active 29 for selective fluorescent “OFF-ON” response toward Ga3+/Al3+ in the presence of other competing metal ions.32 A comparative study suggested that the hydroxyl group played a vital role in the sensing mechanism by providing a platform to bind with the metal ions. The association constant (Ka) for the probe was calculated to be 1.42 × 105 M−1 with Ga3+ and 1.01 × 105 M−1 with Al3+. Along with growing aggregate size, suppression of PET after binding of probes with the metal ion was the chief contributor toward the enhanced emission resulting in the sensitive detection of the target analytes.

Figure 37. FESEM images of the nano and microstructures of the 47, 49−53 formed in 99.9% f w (10 μM) by a simple dropcasting method. The insets showed the corresponding chemical structures (left) and magnified images (right). Reproduced with permission from ref 41. Copyright 2017 The Royal Society of Chemistry.

In 2017, Nicolas et al. reported a novel AIE-active prodrug (30) and polymerized it through nitroxide-mediated polymerization (NMP) where both the AIE dye and the AMA-SG1 alkoxyamine drugs were introduced into the isoprene polymer framework to obtain the polymers P1 and P2 (Napht-PI) (Figure 27).33 These two AIE active polymers were synthesized by adjusting the isoprene and units of 31 into the polymer chain namely P1 (Mn,SEC = 2100 g mol−1, Đ = 1.15) and P2 (Mn,SEC = 3700 g mol−1, Đ = 1.20). The AIE studies of 31, P1,

Figure 36. Chemical structures of luminogens (47, 49−53). Digital photographs of compounds 47, 49−53 under UV light (365 nm) irradiation and white light irradiation. Reproduced with permission from ref 41. Copyright 2017 The Royal Society of Chemistry. M

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Figure 38. Chemical structures of luminogens (54−61).

Figure 39. Chemical structure of 62 and the scheme showing synthetic route to the corresponding polymers and fluorescence images of polymers in pure DMF and DMF/ethanol and DMF/water mixtures. Reproduced with permission from ref 43. Copyright 2012 The Royal Society of Chemistry.

and P2 were performed by changing THF and water mixtures. Including the 31 monomer, both the polymers (P1 and P2) showed good fluorescence enhancement on increasing the f w in the THF solution (Figure 28). However, 31 exhibited high fluorescence in 90% f w and the emission drastically decreased at 100% f w, which could be due to the change in aggregate morphology. The polymer nanoparticles were successfully utilized for cell imaging investigation that allowed them for precise intracellular visualization in various cell lines. Furthermore, the AIE based prodrug polymer nanoparticles were synthesized by conanoprecipitation of P2 (10.8 wt %) with CdA-digly-PI (P3, Mn = 5000 g mol−1, Đ = 1.20). The prodrug nanoparticles were thus taken up by L1210 cells and gathered into the lysosomes. The cell cytotoxicity of the prodrug nanoparticles were also examined through MTT assay toward cancer cells that justified their biocompatibility for therapeutic delivery and fluorescent labeling.

Figure 40. (a) Graphical representation of the electrospun fluorescent porous fibers. (b) Laser confocal microscopic images of 3D fluorescent porous PMMA fibers. (c) Hydrophobic and oleophilic characteristic of the electrospun fibrous and porous PMMA membrane. Rhodamine B was added in the water droplet to make difference with the clear silicon oil. Reproduced with permission from ref 44. Copyright 2014 The Royal Society of Chemistry.

3. NIS WITH HETEROATOM SUBSTITUTION 3.1. NIs with Oxygen Atom Substitution (II). Thilagar et al. reported structurally similar core substituted NI derivatives at the fourth position and explored the effect of molecular environment on their photophysical properties.34−38 All NI derivatives and their solid state fluorescence images are given in Figures 29 and 30. It was observed that the AIE/AIEE property along with the aggregated and solid state quantum yields of the NIs depend on their extent of molecular stiffness and intermolecular interactions. The photophysical, structural and computational study revealed that the pendant substituents affected

the intermolecular interaction (π−π stacking) deeply in their condensed state by modulating the electronic environments that controlled the fluorescence behavior of these congeners in their aggregated state. It was noteworthy that the BODIPY containing congeners showed fine-tuning in the dual state emission and AIE switching from green to red via regular structural perturbation (Figure 31). Through the comprehensive N

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Figure 41. (a) Oil adsorption and desorption process for porous PMMA fibers. (b) Switchable emission (off/on) of porous PMMA fibers based on oil adsorption and desorption process. The fluorescent images were obtained under 365 nm UV irradiation. (c) Plot showing the capacity of oil adsorption and desorption of porous PMMA fibers with 10 cycles. (d) Fluorescence intensity and corresponding images of porous PMMA fibers with 10 cycles based on oil adsorption and desorption. Reproduced with permission from ref 44. Copyright 2014 The Royal Society of Chemistry.

Figure 42. Chemical structure of 63 and its 64 polymer with DFT optimized structure of the monomer. Reproduced with permission from ref 45. Copyright 2013 The Royal Society of Chemistry.

studies of a series of NIs, the condensed-state luminescence characteristic was correlated with their structural conformation. It was also established that the emission properties of small molecules could be fine-tuned through systematic minor structural variations. Apart from the study of structure property relationships, the same group also tried to explore the possible application of the congeners. Considering their flexibility and fluorescence quantum-yield correlation, sulfur containing 35 was chemodosimetrically used to detect Hg(II) in aqueous solution.35 The BODIPY derivatives were also found to have the potential to image cytosol localizations without affecting the cell morphology (Figure 32). The same group again applied a straightforward approach to generate white-light from the NIs.38 In recent decades, development of new white-light emissive molecules has become an interesting research area because of their extensive applications in optoelectronic devices. Although several new strategies have been developed to achieve white-light, the development of unique emissive materials with white-light emission in water has huge biological importance. A new and simple strategy was developed to modulate the color of emissive aggregates by

Figure 43. Structures of fluorescent probe 65−67 and suggested mechanisms for the AIE and TICT processes in 65. Reproduced with permission from ref 46. Copyright 2014 The Royal Society of Chemistry. O

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devices. The level of CPL properties are generally estimated by the luminescence dissymmetry factor (glum), which is equal to 2(IL − IR)/(IL + IR) = 2ΔI/I, where IL and IR signify the luminescence intensities of left CPL and right CPL, respectively. Figures 33a and 33b showed the AIE study of 45, in THF and water mixtures. The PL spectra of 45 exhibited the emission peak at 466 nm in THF solution. Upon increasing the water content from 0 to 70% ,the fluorescence intensity of 45 was quenched because of the polarity-induced fluorescence quenching. Interestingly, when water content reached above 70%, the fluorescence intensity enhanced further and increasing the water content up to 95% the fluorescence becomes brighter with 24 nm red-shift, which can be attributed to AIE active group of NI, and acting as a chromophore herein. The fluorescence quantum yields exhibited by 45 in THF and 95% f w in THF were 7.4% and 13.9%, respectively. To obtain the mechanistic insight of the reversal variation of the CPL signals, the congeners were subjected to theoretical calculations that validated the presence of two different stable conformations of 45 and 46 with variable dihedral angles of the binaphthyl groups in solution and aggregated state. Iyer et al. designed and synthesized three V-shaped NI derivatives (47, 48, and 49) substituting quinoline and naphthalene moieties at its fourth position (Figure 34). All the molecules showed AIE/AIEE properties with unexpected self-assembly behavior.40 In this study, it was demonstrated how a small change in the molecular structure can give rise to highly diverse photophysical and self-assembly properties. The quinoline substituted NIs formed highly fluorescent “‘nanoribbon”’ like structures in aqueous media, whereas other derivatives formed unsymmetrical nanoparticles (Figure 35). By virtue of the single crystal X-ray studies (Figure 34), the classical head-to-tail π−π stacking was revealed to be the main driving force for the unique self-aggregating behavior with J-type aggregation. Through a systematic and comparative mechanistic study, it was confirmed that the N atom in the hydroxyquinoline moiety is responsible for its diverse properties compared to the other congeners. The highly fluorescent nanoribbons were applied for the highly sensitive and selective detection of multifunctional nonheme protein ferritin (Ksv = 0.83 × 107 M−1) with a LOD of 0.67 nM (0.33 ng mL−1) in aqueous media. The nanoribbons also had the capability to induce conformational variations in their secondary structure that could help to study the protein intermediates. Collectively, these results could improve the fundamental knowledge to tune the photophysical and self-assembly properties of small molecules.

employing a complementary AIE pair in aqueous media through this work. To evaluate the concept, the blue emitter 32 and a weak red emitter boron dipyrromethene derivative (BDY) were taken together. Mixing 32 and BDY generated white-light in THF:H2O (1:9 v/v) mixture by the formation of stable nanoaggregates. These nanoaggregates were highly stable at neutral pH and can image live cells efficiently in multiple color. Furthermore, using single excitation energy, they achieved the three primary colors of different energies. The primary advantages of the reported system were to generate white-light in aqueous media, which were highly reproducible along with safer and cheaper handling. On the way to explore the versatility of NI derivatives, Cheng et al. reported four chiral binaphthyl-based molecules (45 and 46) by integrating the AIE-active NI groups, that showed reverse circularly polarized luminescence (CPL) signals from solution to aggregated state.39 Chiral emissive organic compounds with CPL properties are of fundamental importance and have potential application in the field of biosensors and photonic

Figure 44. Proposed binding model of 65 with Hg2+. (a) Bright-field photographs of HeLa cells incubated with 65 (10 μM) in DMEM (containing 5% DMF) for 30 min, with two times washing. (b) Fluorescence image of a. (c) Overlay of a and b. (d) Bright-field image of HeLa cells incubated with 65 (10 μM) in DMEM (containing 5% DMF) for 30 min, with two times washing, and then treated with Hg2+ (5.0 equiv). (e) Fluorescence photographs of d. (f) Overlay of d and e. Reproduced with permission from ref 46. Copyright 2014 The Royal Society of Chemistry.

Figure 45. Chemical structures of 68−74. P

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Figure 46. (a) Emission spectra of 68 in 12 different solvents having different polarities (concentration = 10 μM, λex = 367 nm), right side is the corresponding digital images under UV irradiation of 365 nm. (b) Emission spectra of 68 in THF with different f w at concentration = 10 μM, λex = 367 nm. (c) Digital photographs at different f w. Reproduced with permission from ref 47. Copyright 2012 The Royal Society of Chemistry.

Figure 47. (a) Normalized fluorescence spectra of 69 in various solvents. (b) Digital photographs of 69 in various solvents and in the solid state at 365 nm UV light illumination. Plots of emission spectra areas of 69 versus f w in (c) CH3OH−H2O and (d) in THF−H2O mixture. The digital images of 69 in (e) CH3OH−H2O and in (f) THF−H2O mixture under 365 nm UV light illumination. Reproduced with permission from ref 48. Copyright 2013 The Royal Society of Chemistry.

In another study, Iyer et al. formulated a new methodology to fine-tune photophysical and nanomorphological properties by varying nonconjugated pendant chain.41 By synthesizing a series of six angular “V” shaped NI AIEEgens, (Figures 36 and 37) it was concluded that the N atom acts as a triggering unit whereas the pendant chain behaves as a tuner moiety. The NIs, with similar electronic states and aromatic cores, showed

unexpected tuning of the nanomorphologies and condensed state emission colors. Various experimental and theoretical studies confirmed that the pendant chain generates different strength of bulkiness around the NI core, which controls the intermolecular π−π interactions resulting in the different solid state emission and nanoaggregate morphology. Comprehensively, these findings establish a simple and unique method to Q

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Figure 50. Confocal microscopy photographs of (a) KB cells and (b) HeLa cells incubated with 10 μM [email protected] for 10 min in PBS (pH 7.4) at 37 °C. (λex = 405 nm, λem = 500 ± 50 nm). Reproduced with permission from ref 49. Copyright 2017 Elsevier.

concluded the involvement of multiple mechanisms such as PET, resonance energy transfer (RET) and disaggregation of the nanoaggregates. Fluorogens having extremely pretwisted geometries and easily tunable ICT characters are very promising materials for sensing and electroluminescence (EL) applications. In their study, Lu and co-workers demonstrated for the first time that a C−O bond could assist as the central bond to build new TICT for D−A systems by using 4-aryloxy-NI derivatives as the molecular framework.42 Quantum chemical and photophysical studies endorsed that a stable TICT state was formed in these compounds owing to the rotation around C−O bonds. More importantly, the TICT can be tuned readily due to the strong steric interactions between the aryl ring and the NI systems along with the structural modulation of the aryl moiety. Among all the synthesized congeners 54−61 (Figure 38), whose bridging Ar groups possess gradually increasing interannular twisting angles but weakened electron-donating ability, exhibited progressively weakened TICT features. The 58 with fluorene bridging possessed lower rotational freedom leading to strong TICT characteristic. Crystallographic analysis and theoretical computations were carried out to gain insights into the TICT process, where 58 was found to have highly pretwisted molecular conformation (64−89°dihedrals between its fluorene and NI units), that aroused from the bulkiness generated by the corresponding H atoms of the NI and C atoms of the fluorene units. Such geometrical properties led to enhance the AIEgenic characteristic of 58 even in less-polar toluene and nonpolar solvents. Furthermore, the highly pretwisted ground state geometries of 58 makes an appropriate candidate for high-performance optoelectronic application with good EL performance. The nondoped OLED was fabricated with ITO/MoO3 (7 nm)/ TAPC (40 nm)/mCP (10 nm)/58 (10 nm)/Bphen (40 nm)/Mg:Ag (100 nm) device configuration. 58 exhibited the maximum brightness of 4780 cd m−2, external quantum efficiency of 1.6%, maximum power efficiency of 2.8 lm W−1, turn-on voltage of 3.0 V, maximum current efficiency of 3.0 cd A−1, and CIE1931 coordinates (0.17, 0.27) at 4−8 V. 3.2. NIs with Nitrogen Atom Substitution (III). Lu et al. developed a new and simple approach to formulate AIE polymers through atom transfer radical polymerization (ATRP) by using an AIE initiator.43 By using 62 as an ATRP initiator,

Figure 48. Living HepG-2 cells are incubated with 5 μM of 69 for 30 min and 5 μM of DiI (a commercial cell membrane imaging dye) for 15 min in DMSO-RPMI-1640 (1:49, v/v) at 37 °C. (a) Confocal fluorescence photographs with 69 (green, λex = 405 nm, λem = 480 ± 50 nm). (b) Confocal fluorescence image using DiI (red, λex = 543 nm, λem = 600 ± 50 nm). (c) Overlap of a and b. (d) 3D fluorescence photographs of panel c. (d) xy image, where xz and yz panels displayed the xz and yz cross-sections measured at the line displayed in panel xy, respectively. Reproduced with permission from ref 48. Copyright 2013 The Royal Society of Chemistry.

Figure 49. (a) Schematic representation of 70 (NI-1) coated with SiO2 to fabricate [email protected] nanocomposite. (b) TEM image of [email protected] nanoparticles. (inset: DLS of [email protected] in water). Reproduced with permission from ref 49. Copyright 2017 Elsevier.

precisely control the emission colors and nanomorphologies of small molecules via variation of the nonconjugated alkyl chain. Again the quinoline substituted NIs were found to detect phenolic nitro-explosives selectively in aqueous media. The sensing mechanism was studied extensively which R

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Figure 51. Normalized fluorescence spectra of (a) 71 and (b) 72 in various solvents and digital photographs of 71 in various solvents under 365 nm UV illumination. Reproduced with permission from ref 50. Copyright 2016 The Royal Society of Chemistry.

Figure 52. Emission spectra of (a) 71 and (b) 72 in the CH3OH−H2O mixture with varying f w. (c) Plots of fluorescent areas of 71 and 72 versus the f w in the CH3OH−H2O mixture (d) Digital photographs of 71 and 72 with different f w under UV illumination at 365 nm. Reproduced with permission from ref 50. Copyright 2016 The Royal Society of Chemistry.

AIE property, this strategy also simplified the fabrication process with good film forming characteristic. The AIE study of the polymers were carried out in DMF and water mixture where the polymers were less or nonemissive in DMF. The PL intensity was increased in polymer aggregated state. The PL intensity increased from changing DMF to water 155-fold for PS, 65-fold for PMMA and 10-flod for PHEMA. As shown in the Figure 40 among the synthesized polymers, PMMA polymer based porous fibers with large surface areas were synthesized by electro spinning technique.44 The porous fibers were found to absorb oil efficiently. The PL intensity dramatically reduced after oil adsorption because of the

different monomers like methyl methacrylate (MMA), styrene (St), and 2-hydroxyethyl methacrylate (HEMA) were polymerized under moderate conditions to get PS, PMMA, and PHEMA polymer with AIE characteristic respectively (Figure 39). It was realized that the AIE effect could be enhanced by introducing the AIEgenic initiator at the end of a polymer chain. The monomer was designed strategically to achieve both AIE and intramolecular charge transfer (ICT) characteristic. Such molecules could hamper the intermolecular π−π stacking and enabled them to emit efficiently in their condensed phase. This π−π stacking was even stronger after introducing them into the polymeric chain. Along with the amplification in the S

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Figure 53. (a) Emission spectra of 73 measured in water/THF mixture solvent with varying f w. The inset: the variation of emission with different f w. (b) Schematic illustration of the proposed intermolecular interaction mode and 1H NMR spectra of 73 (10 μM) is with and without TNP in CDCl3. Reproduced with permission from ref 51. Copyright 2016 Elsevier.

It was realized by the same group (Lu et al.) that, although the number of luminogens were very few, the AIE effect could be preserved and also be improved by the efficient wrapping of flexible chains. In this study, they increased the number of anchoring group in the polymer chain.45 They designed a monomer with pyrazoline and NI units (Figure 42) and using this monomer a homopolymer was synthesized via atom transfer radical polymerization (ATRP). In this report, the authors studied the aggregate properties and the ICT process was found to be enhanced through AIE process, along with two-photon absorption (TPA) properties in the monomer and its homopolymer. The NI ring attached with the pyrazoline ring was having good conformational flexibility with a dihedral angle of 31.25°. As a consequence, the molecule preferred a nonplanar conformation which probably blocked the π−π intermolecular interaction in their condensed state. The aggregation properties of both monomer and homopolymers were investigated extensively in various solvent systems. As the polarity of solvent was increased, the fraction of the ICT state also increased with the decrease of the LE state. In extremely polar solvents, the ICT state became the prime emitting state leading to very low fluorescence intensity and quantum yield. However, the emission and absorption spectra were red-shifted in the aggregated state, demonstrating the AIEE phenomenon. They concluded that the polymerization can enhance the TPA property. As compared to that of the 63, the TPA characteristic of the homopolymer was considerably higher both in toluene and in aggregated state. The 64 polymer in toluene displayed two-photon fluorescence (TPF) with high illumination. Because of the steric hindrance of 64 polymer chains, it had much higher TPA cross-section value (983 GM) than that of monomer in toluene (22 GM). In the aggregated state, the

Figure 54. Mechanistic overview of the AIE-based fluorescent rotor (74). AIE properties. (A) Emission spectra and (B) emission intensity of 74 with change in the f w from 0 to 99% in DMSO solution. [74] = 10 μM. Reproduced with permission from ref 52. Copyright 2016 The Royal Society of Chemistry.

swelling porous fibers (Figure 41).44 This adsorption was reversible that could give rise to new directions regarding the utility of these new materials.

Figure 55. Chemical structures of 75 and 76. (a, b) ORTEP diagrams and (c, d) crystal packing of 76a and 76b. Reproduced with permission from ref 53. Copyright 2017 The Royal Society of Chemistry. T

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Figure 56. PL spectra and relative emission intensity of (a, b) 75a and (c, d) 75b, (e, f) 76a, and (g, h) 76b in THF at different f w. The photographs were taken under 365 nm UV illumination; the number specifies the computed quantum yields using an integrating sphere. Reproduced with permission from ref 53. Copyright 2017 The Royal Society of Chemistry.

red-shift observed in their wavelength, due to the more polar environments that can facilitate formation of TICT. When f w were increased, the PL intensities were enhanced due to the AIE effect. These fluorescent probes were applied in the live cell to monitor the presence of Hg2+ and its quantification as well (Figure 44).

4. NIS WITH C−C AROMATIC SUBSTITUTION (IV) Zhu group designed a simple D−A system (68; see structures for 68−74 in Figure 45) using NI and TPE moieties with dual phenomenon.47 In this system, NI facilitated the intramolecular charge transfer (ICT) phenomenon because of its electronaccepting capability, whereas the TPE moiety acted as dual activator for ICT and AIE. This designed system had strong solvatochromism properties with emission covering almost the entire visible region (Figure 46a). These findings presented the first example of a NI-TPE based fluorogen demonstrating both ICT and AIE phenomenon without the presence of any additional electron donating moieties in the molecule. THF and water solvent mixtures were selected for the AIE study (Figure 46b, c). This study concluded that this TPE-NI fluorophore exhibited the ICT and AIE phenomena. In THF solution the fluorophore showed yellow color fluorescence with 7.1% quantum yield. Upon increasing the water ratio, the emission intensity was reduced with remarkable red-shift (∼80 nm), because of the increasing solvent polarity in the system and ICT mechanism. Furthermore, on increasing the water content up to 80% and 90% the fluorescence intensity was enhanced with up to 20.4% quantum yield in 90%, because of the nanoparticle formation. Li et al. demonstrated tracking of cell membrane using a new NI derived AIE active organic dye (69). Because of the TICT activity, this organic dye showed strong solvatochromic effect (Figure 47a, b).48 This was confirmed by studying the aggregation behavior in different solvent systems (Figure 47c-f). The TICT emission was observed in pure THF solution which decreased by the addition of f w up to 50%. However, no such TICT emission was seen in methanol and water mixtures. In both the solvent systems, emission enhancement occurred at higher f w, which could be attributed to the AIE characteristics. The fluorophore 69 exhibited higher fluorescence quantum yields in 90% water in THF (72.1%) or CH3OH (71.9%) and as well as in solid state (73.0%), as compared to pure THF or CH3OH solutions (Figure 48). The specified bioprobes with

Figure 57. Chemical structures of 77−81. (a) The normalized emission spectra and (b) the CIE chromaticity coordinate of dye 77−80 in the solid state. Inset: solid-state fluorescence images under the UV lamp. Reproduced with permission from ref 54. Copyright 2016 Elsevier.

polymer 64 had ∼4.98-fold higher TPA action cross-section as compared to pure DMF. This study confirmed that TPA can be amplified by incorporating the 63 into a polymeric chain and the amplification is directly proportional to the percentage of luminogen in the polymer backbone. Thus, the application of an AIEactive 64 polymer in TPA or TPF studies could emerge as a new technique to gain improved cross-section TPA materials. A new versatile NI-based fluorescent dye 65 was reported by Yang et al. that displayed outstanding performances for the recognition of Hg2+ along with both the TICT and AIE characteristic in aqueous solution.46 Dye 65 showed high selectivity and sensitivity toward Hg2+ with “turn-on” emission characteristic in aqueous solution. The fluorescence enhancement 65 with Hg2+ concentration followed a linear trend which indicated that, this method could be applicable for Hg2+ quantification. To find out the sensing mechanism, they have also synthesized two model compounds 66 and 67 (Figure 43). To explore the AIE characteristics they have chosen THF and water mixture. When f w changes from THF to 70% water the PL intensities of these compounds were decreased with slight U

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Figure 58. Suggested dual-switch sensing mechanism of probe 81 for the detection of (a) Hg2+ and (b) Fe3+. Reproduced with permission from ref 55. Copyright 2017 Elsevier.

Figure 59. Fluorescence photographs of (a) dye 77 in MCF-7 breast cancer cells and (b) dye 78 in HeLa cells. Reproduced with permission from ref 54. Copyright 2016 Elsevier.

This process was attributed to the TICT. Apart from good optical properties, these molecules showed sensitive fluorescence response toward nitroaromatic explosives. It was observed that the congener with SiMe3 group exhibited enhanced optical properties and higher sensitivity toward nitroaromatic detection. Similarly, Zhang and co-workers designed another AIEE active NI based D−A fluorescent system (73) by substituting anthracene unit and employed them to detect picric acid in aqueous solution (LOD = 0.47 μM).51 The AIEE activity of the fluorophore was investigated in THF and water mixtures (Figure 53a). The fluorophore became non emissive when f w reached 50%, due to the dipole−dipole interaction between the fluorescent molecule with solvent molecules in excited state. After f w exceeded >50%, the fluorescence intensity increased up to 100%. The typical intramolecular charge transfer (ICT) emission was blocked because of the proton transfer from picric acid to 73 as confirmed by NMR analysis and contributed toward the sensing mechanism (Figure 53b). Xu and co-workers designed smart material based on bisnaphthalimide (74) where two naphthalimide cores were conjugated at the fourth position via a twisted C−C single bond.52 The molecule behaved as a double-channel rotor because of the presence of two naphthalimide planes. The bisnaphthalimide derivative showed emission at the shorter wavelength

low cytotoxicity and high photostability could track the living cells for nearly 100 h indicating its efficient long-term staining capability as compared to the common organic dye. Chang et al. reported a similar fluorophore to 69 by replacing the naphthalene group with pyrene units (70).49 The pyrene substituted NI probe surface was coated with SiO2 and the [email protected] nano structure was fabricated (Figure 49). It was observed that the obtained nanomaterial exhibited AIE phenomenon with remarkable antiphotobleaching ability and biocompatibility. The nanomaterial was found to light up the mitochondria efficiently and thus could be utilized as a mitochondria imaging reagent (Figure 50). Feng et al. designed and synthesized two NI congeners from hexaphenylbenzene (71 and 72).50 The traditional fluorescent core was converted to AIEgenic molecule based on the dendritic polyphenyl structure. The synthesized molecules showed excellent solvent-induced fluorescence variation from deep blue to green (Figure 51). To find out the AIEE nature of both 71 and 72, they carried out PL studies in CH3OH and water mixtures (Figure 52). For both fluorophores when water content changed from 0 to 40%, the fluorescence intensity slowly decreased. Suddenly the emission intensity increased with blue-shift at 50% f w, and when f w changes to >50% the emission intensity decreased, because of the nanoparticle formation (as confirmed by the SEM and DLS analysis). V

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Figure 60. Chemical structures of 82−86. Plots of FONs for 84; (a) plots of the fluorescence quantum yields of different solvent fractions versus [H+] values. (b) Fluorescence changes for 84 under 0, 25, 50, 75, and 100 percentages of 10 mM HCl aqueous solutions in THF (λex = 400 nm). Insets: digital pictures and TEM images of nanoparticles achieved at 10 mM HCl aqueous solutions in THF, 25/75 v/v, and scale bar 50 nm. (c) Corresponding bright-field picture (left) and fluorescence photographs (right, light path through a 380/10 nm bp filter and fluorescence was measured and filtered through a 450 nm lp filter) of MCF-7 breast cancer cells incubated with 10 μM 82 (NIM-1), 83 (NIM-2), and 84 (NIM-3) compounds for 4 h, respectively. Reproduced with permission from ref 14. Copyright 2011 The Royal Society of Chemistry.

in its twisted state, whereas emission at longer wavelength was observed in its planar state (Figure 54). In DMSO solution, because of dynamic rotation of the naphthalimide units, the molecule was almost nonemissive, but in case of solvents with high viscosity or in poor solvent where it formed nanoaggregates, it showed strong emission character because of the restriction of intramolecular rotation (RIR) effects. The AIE activity was investigated in three different solvent systems, including THF/water, DMSO/water (Figure 54), and acetonitrile/water in varying ratios. It was observed that formation of a more polar nonradiative ICT state occurred in DMSO with weak ICT fluorescence, whereas ICT fluorescence was quite high in THF and acetonitrile. But, the synergetic effects of intramolecular planarization and RIR led the molecule to emit intensely at longer wavelength by the addition of water due to aggregate formation. Thus, in this study, a simple fluorometric method for the detection of viscosity has been developed by using the bisnaphthalimide with dramatic variation in both emission intensity and wavelength. The fluorogen produced a logarithmic response to the viscosity of a water/glycerol system with varying ratios. Additionally, the fluorogen demonstrated high sensitivity toward temperature-related viscosity disparities that could also work in the presence of common fluorescent dyes.

Thus, the property could be of high significance in many biological and mechanical systems, as temperature always alters the surrounding viscosity. Recently, Iyer et al. designed and synthesized four D−π−A novel organic molecules (75−76) based on NIs and monosubstituted dibenzofulvenes and studied the effect of heavy atom and other photophysical properties (Figure 55).53 Despite the very similar structural building of the four NIs, two compounds exhibited the AIEE phenomena, whereas remaining two compounds displayed weak AIEE and ACQ property (Figure 56). The four luminogens displayed different photophysical properties based on the bridge (thiophene and phenyl) between D and A. The AIEE active luminogens displayed orange to red emission (575 and 602 nm) with large bathochromic shifts (35 and 112 nm) in the aggregated state owing to ladder type J-aggregate formation with high quantum yields of 84.10% and 65.65% for 75a and 75b respectively. The nanoaggregate formation was confirmed by the FESEM and DLS analysis. In contrast, the phenyl bridged derivatives showed poor AIEE characteristic (76a) in blue region and ACQ nature (76b) due to the strong C−H···π intermolecular interactions (confirmed by the single crystal X-ray study). Additionally, theoretical analyses were carried out to support W

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that the dye 77 and 78 displayed selective recognition toward Hg2+ ions due to the presence of terminal N,N-dimethylethylenediamino unit whereas 81 showed selective recognition toward both Fe3+ along with Hg2+ due to the presence of dipicolylamine moiety. The congeners showed high fluorescence emission in their solid state with tunability. Both the photoinduced electron transfer (PET) and fluorescence resonance energy transfer (FRET) endorsed a ratiometric detection of Hg2+/Fe3+ in 81 with a detection limit of 2.72 × 10−6 M and 5.7 × 10−7 M in EtOH/PBS buffer (1:1, v/v, pH = 7.4) solution respectively (Figure 58). Apart from the detection of Hg2+, the dye 77 and 78 were also employed to image MCF-7 breast cancer cells and HeLa cells and certified their potential in biology (Figure 59). A series of novel NI derivatives (82−86) with D−A architecture were reported Chang et al. by substituting 4-methoxystyrene, 4-(N,N-diphenylamino)styrene, 4-nitrostyrene and 4-hydroxystyrene moieties and presented their absorption and PL properties.14 Their AIEE characteristics were explored and their practicability was illustrated through cellular imaging. The styrene derivatives substituted 83 and 84 displayed low fluorescence in dilute solutions but proficiently emitted in aggregated state (Figure 60a, b). The emission intensity of 84 amplified drastically when aqueous acid solution was added because of the formation of self-assembled fluorescent nanoparticles by the protonated 84 (84-3H+). All the derivatives were well dispersed in the cytoplasm with good cell penetrability. Owing to their AIEE properties, bright cellular imaging of Human breast adenocarcinoma cell line (MCF7) was achieved by these probes at different emission wavelengths at a fixed excitation wavelength (Figure 60c). 82 and 83 (Figure 61) were cocultured with MRC-5 normal lung fibroblast cells and CL1−0 lung cancer cells and the results indicated that, although 82 was not capable to differentiate normal cells and cancer cells, molecule 83 was found to disperse in the cytoplasm of normal living cells whereas they get accumulated in cancer cells resulting in the bright imaging capability. These different cellular staining arrays signified that 83 could be employed to discriminate cancer cells from normal cells. Panchenko and co-workers synthesized a series of styryl NI derivatives (87−89) and investigated their photophysical properties in detail considering their pronounced potential of being used as imaging agents in vivo (Figure 62).56 The key relaxation pathways of the local excited singlet state of the NIs were found to be fluorescence, E,Z-photoisomerization and formation of the TICT state that could be controlled through solvent polarity or structural modulation. All congeners showed a positive solvatochromism in the steady-state fluorescence and absorption spectra. In nonpolar solvents like cyclohexane and toluene, isomerization took place effectively where the planar local excited (LE) states were dominant. The introduction of high polar solvent was favored by the twisting between styryl and NI fragments leading to the formation of a TICT state and was confirmed through quantum-chemical calculations and NMR spectroscopy analysis (Figure 63). Organic light-emitting diodes (OLEDs) have been considered as the “next generation of lighting technology” and the “third generation of flat panel displays”, that have attracted much attention in both industrial and scientific societies. Extremely proficient fluorescent OLEDs are highly favorable for display applications because of their quick response time, longer operational lifetime, and comparatively low efficiency roll-off at high current densities. In this respect, Yu et al.

Figure 61. Confocal microscopy photographs of cocultured CL1−0 lung cancer and MRC-5 normal lung fibroblast cell lines incubated with 10 mM probe for 4 h, and 405 nm light source was applied to visualize the cells. Compound 82 (NIM-1): (a) Bright-field image; (b) spectra measured at 450−560 nm in PMT 1; (c) 530−650 nm in PMT 2; (d) merger of b with c; (i) λ scanning from 460 to 650 nm with 5 nm integration. Compound 83 (NIM-2): (e) Bright-field image; (f) spectra measured at 450−590 nm in PMT 1; (g) 560−740 nm in PMT 2; (h) merger of f with g; (j) λ scanning from 450 to 780 nm with 10 nm integration, inset photo is the zoom in of image h but filter cut at 560 nm. Fifty individual cancer and normal cells were taken and the average intensities were plotted to get the spectra. Reproduced with permission from ref 14. Copyright 2011 The Royal Society of Chemistry.

Figure 62. Chemical structures of 87−89.

the photophysical characteristic of the AIEEgens. Also the HOMO and LUMO energy levels were calculated by theoretical study and cyclic voltammetry. The thermal behavior of the NIs were studied by TGA and DSC and the results showed good thermal stabilities.

5. NIS WITH C−C DOUBLE AND TRIPLE BOND SUBSTITUTIONS (V AND VI) A series of NI-rhodamine dye (77−81) was designed and synthesized by Qian et al. by varying the terminal substituent at the fourth position of NI core.54,55 The rhodamine moiety was used as a rigid and bulky substituent to boost the AIE characteristic. All the NI-rhodamine congeners exhibited fluorescence emission in the condensed state signifying the AIEE phenomena (Figure 57). Although the dyes showed fluorescence in their aggregated state, their poor solubility in pure water makes their application limited. Thus, the asprepared dye-doped fluorescent silica nanoparticles (Si-NPs) exhibited good solubility in pure water. It was also observed X

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Figure 63. Aromatic and aliphatic region of the 1H NMR spectrum of compound 89 in toluene-d8 before (top) and after (bottom) illumination at 436 nm. The Z-isomer signals were marked with color. [89] = 2 × 10−2 M. Reproduced with permission from ref 56. Copyright 2017 the PCCP Owner Societies.

Bphen (40 nm)/Mg:Ag (200 nm). As a result of the AIE behavior of the guest molecule, and the effective energy-transfer between the structurally similar host and guest as well, the 6 wt % heavily doped NI-based devices showed good performance, with maximum brightness of 6250 cd m−2 and current efficiency of 3.13 cd A−1. To prove that 92 was a better host for 91, they have also fabricated OLED device by using Alq3 instead of 92 because the host was having much inferior EL properties despite its comparatively efficient spectral match, which could be attributed to the insufficient energy transfer between Alq3 and 91 and achieved maximum brightness whereas the luminous efficiency was 1160 cdm−2 and 0.75 cd A−1, respectively. Thus, it could be concluded that the design of suitable host/guest pair for efficient energy transfer is of extreme importance for the enhanced device performance and also certified the naphthalimide derivatives as promising host/guest material for fabrication of heavily doped red OLED. They have also fabricated nondoped OLEDs with ITO/NPB (30 nm)/91 (20 nm)/Bphen (40 nm)/Mg:Ag (200 nm) device configuration. These devices gave maximum brightness and luminous efficiency of 3520 cdm−2 and 0.55 cd A−1 respectively. According to the electroluminescence (EL) mechanism, OLEDs are of two types, namely fluorescent (FOLEDs) which

Figure 64. Chemical structures of fluorophores 90−94.

developed AIE active fluorophores for various roles in OLED applications (90−94) (Figure 64).57 Using this AIEgen they fabricated the nondoped and heavily doped red OLEDs. They designed two guest fluorophores with NI and fluorene moiety bridged through an ethenylene bond to form a red D−π−A luminogens. One of them (91) was found to be AIE-active, which makes it a potential nominee to be a guest to fabricate heavily doped red OLEDs (Figure 65). To procedure an effective energy transfer guest/host pair, a structurally similar green host material 92 was synthesized. The device configuration was: ITO/NPB (30 nm)/CBP (2 nm)/92:91 (x wt %) (20 nm)/

Figure 65. (a) Normalized absorption and emission spectra of 90 and 91 in polycrystalline powder state and in THF solution (10 μM). Insets: images of the polycrystalline powder of (A, B) 90, (C, D) 91 under white light (top) and UV light at 365 nm (bottom). (b) Emission spectra of 91 in acetonitrile at different f w. (Concentration of 91: 10 μM, λex = 460 nm). Insets: digital photographs of 91 in acetonitrile/water mixture under UV light at 365 nm. Reproduced with permission from ref 57. Copyright 2014 Elsevier. Y

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ACS Applied Materials & Interfaces is generally limited to 25% internal quantum efficiency (IQEmax) and phosphorescent ones (PhOLEDs), although a high IQEmax of 100% could be attained, but the use of rare metal complexes make them costly.58−60 However, through several mechanisms like thermally activated delayed fluorescence (TADF), triplet fusion delayed fluorescence (TFDF), and hybridized local and charge-transfer excited states (HLCT), FOLEDs can be harvested via both singlet and triplet excitons. For TADF-OLEDs, design of small singlet−triplet energy gap (DEST) with high radiative rate within TADF is quite hard, whereas for HLCT materials, the internal conversion from Tn to Tm states (m < n) should be blocked by disobeying Kasha’s rule.61,62 Thus, the balanced molecular design of HLCT compounds are still highly challenging. However, for OLEDs constructed on the basis of TFDF compounds, their IQEmax could reach up to 62.5% by the upconversion of triplet into singlet efficiently through the TTA process.63−66 The triplet excitons could harvest efficiently by the host compounds via energy transfer to emitting guest materials. However, small-molecule-based TF compounds are limited to anthracene derivatives, Alq3, and rubrene, whose S1 and T1 states are both of 3ππ* character. In 2014, Lu et al. reported 94 as a promising TFDF-OLED material with ICT properties and small exchange energy but a lower lying 3ππ* state than the 3CT state (Figure 66).58 By using 94 as host material with the same guest material 91, they fabricated device following the previous configuration as ITO/NPB (30 nm)/ CBP (2 nm)/91:94 (6 wt %, 20 nm)/Bphen (40 nm)/Mg:Ag. The orange-red emitting electroluminescent device with a brightness of 16840 cdm−2 and a highest current efficiency of 7.2 cd A−1 achieved was more than 2-fold as compared to their previous report using the same guest material (Figure 66). Lu et al. further reported newly designed 93, an ICT-featured red D−π−A TFDF fluorophore, and used it as a guest material with the 94 host material to fabricate OLED devices (Figure 67).67 As both 93 and 94 were NI derivatives, they could generate a proficient host/guest energy transfer pair and the presence of a large diphenylamine D-moiety in 93 could be equipped with less intermolecular interactions. To find out that 93 was a TADF material capable of harvesting triplet excitons via the TTA process, they fabricated the nondoped OLEDs (Device I) with device configuration ITO/MoO3 (1 nm)/TCTA (40 nm)/ CBP (2 nm)/93 (20 nm)/ TPBI (45 nm)/ LiF (1 nm)/Al (80 nm). The device showed the highest brightness and current efficiency was 5100 cd m−2 and 0.53 cd A−1, respectively. The maximum EQE obtained for this device was 0.59%, which is quite higher than that predicted from the 25% singlet production limit (0.34%). Further, the heavily doped OLEDs were fabricated with two different doping ratios of 93 (1.4 and 6.0 wt %). The 1.4 wt % doped device (Device II) exhibited the yellow color emission at 570 nm, with maximum brightness, EQE and current efficiency of 24900 cd m−2, 2.49%, and 3.19 cd A−1 respectively. Another device (Device III) that was made using 6.0 wt % exhibited the emission at 583 nm with a highest brightness of 31940 cd m−2 and maximum current efficiency of 7.73 cd A−1, and the maximum EQE was 5.83%. Compared to 1.4 wt %, the 6.0 wt % device performance improved because eof the triplet excitons that could harvest effectively not only by the host materials, but also by the guests through the TTA process. These results certified the importance of TFDF in generating proficient OLEDs, and may shed light on the molecular design strategy for host

Figure 66. (a) Current density−voltage−luminance characteristics curves, (b) current efficiency−current density curves for Device III (inset: EL spectra of Device III), and (c) representation of the proposed TTA and energy transfer (ET) processes in Device II through energy level diagram. The energy levels were for 94 (host) and 91 (guest). Reproduced with permission from ref 58. Copyright 2014 The Royal Society of Chemistry.

materials to achieve high-performance OLED devices to match the market demand. AIE materials with intramolecular charge transfer properties are gaining significant attention from both theoretical and experimental researchers owing to their possible applications in optoelectronics and sensors. However, the nonradiative deactivation of AIEgens with the D−A combination in polar solvents was generally attributed to the TICT mechanism. The same group, investigated the nonradiative deactivation mechanism of the prereported AIE-active NI (91) in the polar solution combining the theoretical and experimental observations.68 It was observed that 91 emits green color (530 nm) and exhibited 75% quantum yield in cyclohexane, whereas the emission became invisible in dichloromethane solution. The thorough and systematic investigation on solvent polarity indicated that in the deactivation process, conformational planarization mechanism would be favored by 91. The geometric conformation and the potential energy surface curves of the studied molecule did not support the general TICT phenomena suggested for numerous classical D-π−A systems. The greater reorganization energy in the S1 state and the small energy gap between HOMO and LUMO suggested that changing the solvent polarity from nonpolar to polar could encourage the compound to achieve the planarization. As seen, the substantial red-shift in fluorescence, the reduction in the radiative decay rate and the enhancement in the nonradiative decay rate were witnessed by changing the solvent polarity from nonpolar to polar. These findings could provide better insights into the earlier studies to justify the debate on the deactivation phenomena of the AIE ICT featured luminogens in solution state and could motivate further studies on the decay mechanism of the other AIE systems. Yi et al. reported two NI gelators based on organometallic terpyridyl platinum, which have hydrophobic cholesterol units by varying the alkyl substituents (Figure 68).69 The complex with three tert-butyl units (95a) was found to form stable gel in various solvent (ethyl acetate, alcohol and toluene) with ultrasound irradiation. These gels showed different color and Z

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ACS Applied Materials & Interfaces fluoroscence properties than that of solutions and precipitates. The photoluminescence enhancement of 95a in gel state was due to aggregate formation. The morphology and the surface wettability was tuned through sonication and heating (Figure 69). However, the 95b complex which is not having tert-butyl units displayed inferior gelation capability and solubility along with lower fluorescence quantum yield due to metal−metal and intermolecular ππ interaction. The self-assembled behavior indicated that the gelation and PL properties of complexes were mainly dependent on the steric hindrance of tert-butyl units (Figure 68). Sonication could modify the molecular arrangement of 95a and encourage the hydrophobic and ionic dipolar interactions for gelation. Hence, it changes the photophysical properties of the complex in dense state. This reversible sonication prompted gelation and the PL enhancement could generate new strategies for the application in microfluidic systems in therapeutics. Furthermore, these metallogels could emerge as ideal frameworks for the development of supramolecular emitting materials for displaying information with tunable optical properties.

Generally, a gel exhibits ACQ phenomenon which is undesirable for their light-emitting properties. Yi and coworkers reported AIE-active 4-ethynyl-1,8-naphthalimide based gelators (96 and 97).70 With very high fluorescence quantum yields both in solution as well as in aggregated state, the NI gelator exhibited reversible sol−gel transition and the fluorescent emission had a large red-shift of 80 nm in gel state to that of the solution state (Figures 70 and 71). The NI was able to gelate the polar solvents like EtOH, DMF, ethyl acetate, DMSO, and acetone that were stable at room temperature for more than a week. The hot solution of the NI was blue emitting and became yellow emitting after it was cooled naturally at room temperature for 9 min due to the transition of sol to gel. The aggregation behavior was confirmed by the addition of water that showed similar type of red-shift. The optimized models endorsed the presence of highly planar bulky conjugated structure in 96 and 97, which favored strong intermolecular π−π interactions and played the key role in the formation of organogel. The morphology study showed the formation of microbelts in its gelated state. The organogels also

Figure 67. (a) Current density−luminance−voltage (J−L−V) curves of devices from II to IV and (b) EL spectra of devices from II to V (at 10 V). (c) Graphical representation for the TTA and energy transfer processes in device III. Reproduced with permission from ref 67. Copyright 2015 The Royal Society of Chemistry.

Figure 68. Chemical structure of 95a and 95b with the schematic representation of the gelation mechanism in 95a. (a) Heating−cooling and (b) sonication. Reproduced with permission from ref 69. Copyright 2013 The Royal Society of Chemistry. AA

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Figure 71. (a) Emission spectra of 96 during the sol−gel transition through natural cooling from 120 to 59 °C (Csol = 16 mM; λex = 390 nm). (b) Emission spectra of 96 in DMF (1.0 × 10−5 M) at various f w (λex = 365 nm) and (c) Corresponding photographs of b (the top row was under white light, and the bottom row was under UV irradiation at 365 nm). Reproduced with permission from ref 70. Copyright 2014 American Chemical Society.

Figure 69. (a, b) SEM and (c, d) TEM photographs of 95a in gelated condition made (a, c) by sonication method (0.16 W cm−2, 40 kHz, 30 min, 40 °C), and (b, d) by cooling down from hot solution to room temperature; inset of b is the zoomed view of the nanoparticle of 95a in n-propanol; SEM photographs of 95b after sonication for (e) 60 min and (f) after heating−cooling process in acetonitrile solution; scale bars are (a) 5.0, (b) 2.0, (c) 0.2, (d) 0.1, (e) 2.0, and (f) 20 μm. Concentration: 40 mg mL−1. Reproduced with permission from ref 69. Copyright 2013 The Royal Society of Chemistry.

6. CONCLUSION AND PERSPECTIVES Naphthalimide (NI) compounds are imide-group-containing well-known acceptors and their derivatives have been developed to realize multiple applications over the past several decades. Because of their accepting capacity and high PL quantum yields, NIs have received considerable attention among the scientific community. The AIE activity in NIs opens a new class of AIE-active materials with immense possibilities for various real-world applications both in solution and condensed states. Although TPE, TPP, and HPS derivatives have been established as an efficient and standard luminogenic cores, a large number of research groups have been enthusiastically participating in this area and have designed many new AIE/AIEE-active derivatives. After the first report on NI luminogens, exploration of the aggregation properties of NIs, owing to their wide potential and easy synthetic route, has increased over the years. Multiple research groups have devoted careful efforts to expand the scope of this core as a possible alternative to existing systems by adding crucial research and information to the existing literature. In this review, we have summarized the up to date progress made with the NI core that demonstrates the versatility of this chromophore. We have presented typical examples of different types of NI AIE/ AIEEgens, discussed their high-tech applications as advanced materials along with structure−property relationships. The highly attractive applications of NI luminogens are in the areas of bio- and chemosensors and self-assembly studies. Apart from this, various groups are also exploring the NIs in the field of organic light-emitting diodes, stimuli response materials, in vitro and in vivo imaging of cells, and biogenic molecules. Because of the good biocompatibility, photostability, and highcondensed-state emission behavior, NIs are promising for indepth and long-term bioimaging and tracking applications. Apart from the discussed examples, there are plenty of reported NI derivatives that may show AIE/AIEE characteristics and

exhibited thermally reversible fluorescence from blue to yellow between sol and gel state (Figure 71). Thus, the variation in the fluorescence color between sol and gel could act as a switch for various purposes such as switchable molecular devices and visual recognition sensors.

Figure 70. Chemical structure of 96 and 97. Photographs of sol−gel transition of 96 in DMF at 0.6% concentration (16 mM): (a, c) solution and gel states under white light, respectively; (b, d) solution and gel states under UV irradiation of 365 nm, respectively. Reproduced with permission from ref 70. Copyright 2014 American Chemical Society. AB

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(10) Luo, J. D.; Xie, Z. L.; Lam, J. W. Y.; Cheng, L.; Chen, H. Y.; Qiu, C. F.; Kwok, H. S.; Zhan, X. W.; Liu, Y. Q.; Zhu, D. B.; Tang, B. Z. Aggregation-Induced Emission of 1-Methyl-1,2,3,4,5-Pentaphenylsilole. Chem. Commun. 2001, 1740−1741. (11) An, B. K.; Kwon, S. K.; Jung, S. D.; Park, S. Y. Enhanced Emission and Its Switching in Fluorescent Organic Nanoparticles. J. Am. Chem. Soc. 2002, 124, 14410−14415. (12) Mei, J.; Leung, N. L. C.; Kwok, R. T. K.; Lam, J. W. Y.; Tang, B. Z. Aggregation-Induced Emission: Together We Shine, United We Soar! Chem. Rev. 2015, 115, 11718−11940. (13) Zhao, Z.; He, B.; Tang, B. Z. Aggregation-Induced Emission of Siloles. Chem. Sci. 2015, 6, 5347−5365. (14) Lin, H. H.; Chan, Y. C.; Chen, J. W.; Chang, C. C. AggregationInduced Emission Enhancement Characteristics of Naphthalimide Derivatives and Their Applications in Cell Imaging. J. Mater. Chem. 2011, 21, 3170−3177. (15) Sun, Y.; Liang, X. H.; Zhao, Y. Y.; Fan, J. A Water-Soluble, 1,8Naphthalimide Based Aggregation Induced Synchronous Emission System for Selective and Sensitive Recognition of Casein. Anal. Methods 2012, 4, 4284−4288. (16) Sun, Y.; Liu, Z.; Liang, X. H.; Fan, J.; Han, Q. Study on Photophysical and Aggregation Induced Emission Recognition of 1,8Naphthalimide Probe for Casein by Spectroscopic Method. Spectrochim. Acta, Part A 2013, 108, 8−13. (17) Sun, Y.; Liang, X. H.; Fan, J.; Han, Q. Studies on the Photophysical Properties of 1,8-Naphthalimide Derivative and Aggregation Induced Emission Recognition for Casein. J. Lumin. 2013, 141, 93−98. (18) Sun, Y.; Liang, X. H.; Fan, J.; Yang, X. H. A Highly Selective 1,8Naphthalimide Probe for Recognition of Casein Based on Aggregation Induced Emission Enhancement Characteristics. J. Photochem. Photobiol., A 2013, 253, 81−87. (19) Sun, Y.; Liang, X. H.; Wei, S.; Fan, J.; Yang, X. H. Fluorescent turn-on Detection and Assay of Water Based on 4-(2-Dimethylaminoethyloxy)-N-Octadecyl-1,8-Naphthalimide with Aggregation-Induced Emission Enhancement. Spectrochim. Acta, Part A 2012, 97, 352−358. (20) Soni, M.; Das, S. K.; Sahu, P. K.; Kar, U. P.; Rahaman, A.; Sarkar, M. Synthesis, Photophysics, Live Cell Imaging, and Aggregation Behavior of Some Structurally Similar Alkyl Chain Containing Bromonaphthalimide Systems: Influence of Alkyl Chain Length on the Aggregation Behavior. J. Phys. Chem. C 2013, 117, 14338−14347. (21) Han, C. P.; Huang, T. H.; Liu, Q.; Xu, H. T.; Zhuang, Y. P.; Li, J. J.; Hu, J. F.; Wang, A. M.; Xu, K. Design and Synthesis of a Highly Sensitive ″Turn-On″ Fluorescent Organic Nanoprobe for Iron(III) Detection and Imaging. J. Mater. Chem. C 2014, 2, 9077−9082. (22) Chen, Z.; Wu, D.; Han, X.; Nie, Y. T.; Yin, J.; Yu, G. A.; Liu, S. H. 1,8-Naphthalimide-based Highly Blue-Emissive Fluorophore Induced by a Bromine Atom: Reversible Thermochromism and Vapochromism Characteristics. RSC Adv. 2014, 4, 63985−63988. (23) Cho, D. W.; Cho, D. W. Excimer and Exciplex Emissions of 1,8Naphthalimides Caused by Aggregation in Extremely Polar or Nonpolar Solvents. New J. Chem. 2014, 38, 2233−2236. (24) Bao, Y. Y.; De Keersmaecker, H.; Corneillie, S.; Yu, F.; Mizuno, H.; Zhang, G. F.; Hofkens, J.; Mendrek, B.; Kowalczuk, A.; Smet, M. Tunable Ratiometric Fluorescence Sensing of Intracellular pH by Aggregation-Induced Emission-Active Hyperbranched Polymer Nanoparticles. Chem. Mater. 2015, 27, 3450−3455. (25) Mati, S. S.; Chall, S.; Bhattacharya, S. C. Aggregation-Induced Fabrication of Fluorescent Organic Nanorings: Selective Biosensing of Cysteine and Application to Molecular Logic Gate. Langmuir 2015, 31, 5025−5032. (26) Yeh, M. Y.; Huang, C. T.; Lai, T. S.; Chen, F. Y.; Chu, N. T.; Tseng, D. T. H.; Hung, S. C.; Lin, H. C. Effect of Peptide Sequences on Supramolecular Interactions of Naphthaleneimide/Tripeptide Conjugates. Langmuir 2016, 32, 7630−7638. (27) Srivastava, A. K.; Singh, A.; Mishra, L. Tuning of Aggregation Enhanced Emission and Solid State Emission from 1,8-Naphthalimide

could be extended toward many unexplored possibilities. In this perspective, we have attempted to include all those results where authors have mentioned the aggregation properties of the NIs and their derivatives. Hence, the future of the exponentially spreading research on the AIE/AIEE-active NI family in this decade seems very rich, bright, and multicolored. We eagerly look forward to new findings and developments with these potentially amazing NI derivatives.



AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] Fax: +913612582349. ORCID

Niranjan Meher: 0000-0003-3558-3712 Parameswar Krishnan Iyer: 0000-0003-4126-3774 Author Contributions †

P.G. and N.M. contributed equally to this work.

Notes

The authors declare no competing financial interest.



ACKNOWLEDGMENTS The authors thank the Department of Science and Technology (DST), New Delhi, (DST/SERB/EMR/2014/000034, DST/ TSG/PT/2009/23), DST-Max Planck Society, Germany (IGSTC/MPG/PG(PKI)/2011A/48), and Department of Electronics & Information Technology, (DeitY) 5(9)/2012NANO (Vol. II), for financial support.



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DOI: 10.1021/acsami.7b14473 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX