Fluorescence Color Research Articles

Photomodulation of Charge Transfer through Excited‐State Processes: Directing Donor‐Acceptor Binding Dynamics

AbstractModulating charge transfer (CT) interactions between donor and acceptor molecules may give rise to unique dynamic changes in physicochemical properties, exhibiting great importance in supramolecular chemistry and materials science. In this work, we demonstrate the first instance of reversible photomodulation of donor‐acceptor (D−A) CT interaction in the solid state. Pyridinium‐based chromophore featuring π‐conjugated D−A structures can not only function as a good electron acceptor to undergo photoinduced electron transfer (ET) or engage in intermolecular CT interaction, but also exhibit unique dual emission depending on the excitation wavelengths. The rotatable C−C single bonds within D−A pairs enhance the tunability of molecular structure. Through the synergy of a photoinduced ET and an excited‐state conformational change, the intermolecular CT interaction can be switched on and off by alternate light irradiation to enable reversibly modulation of the affinity between donor and acceptor molecules, accompanied by visual color switching and fluorescence on‐off as feedback signals.

Identification of peripheral nerve functional fascicles in Sprague-Dawley rats by the carbon quantum dot-Annexin V antibody complex

To explore a method to identify the sensory and motor fascicles of the peripheral nerve to achieve accurate peripheral nerve functional fascicle suture. The peripheral nerve Sunderland V injury model, muscle branch of the femoral nerve and saphenous nerve were established in the bilateral femoral nerves of Sprague-Dawley (SD) rats. The specific samples were grouped as follows: the main trunk of the femoral nerve was exposed bilaterally and cut with microscopic scissors in the main trunk of the femoral nerve to prepare a model of Sunderland V injury in the mixed fascicle of peripheral nerves; the muscle branch of the femoral nerve was exposed bilaterally and cut in the middle section of the muscle branch of the femoral nerve to prepare a model of Sunderland V injury in the motor fascicle of peripheral nerves; the saphenous nerve was exposed bilaterally and cut at 1 cm below the patella to prepare a model of Sunderland V injury to the sensory fascicle of the peripheral nerves. A carbon quantum dot (CD)-annexin V antibody complex was prepared and applied to the distal and proximal nerve stumps of the peripheral nerve Sunderland V injury model groups of SD rats. Under the excitation light source of a 380 nm uv lamp, fluorescence color development was observed under a fluorescence microscope after 5, 10, 15, and 20 min. At 5 min, sections of the bilateral femoral nerve trunk, muscular branches of the femoral nerve, and Sunderland V lesion of the saphenous nerve in SD rats were only dark in color under the microscope, and there was no difference in fluorescence. The intensity of the staining increased significantly for 10–20 min. The sensory fascicles and saphenous nerves of the femoral nerve trunk showed blue fluorescence under the CD-Annexin V antibody complex staining, while the motor fascicles and muscle branches of the femoral nerve trunk showed no fluorescence. Fluorescence intensity gradually decreased after 20 min of staining. There was no significant difference in the staining intensity at 5, 10, 15, and 20 min in each group. Our results suggest that the CD-Annexin antibody complex can be used to identify functional fascicles of peripheral nerves in SD rats.

Heterostructure of Hydrogen‐Bonded Organic Frameworks for White Light Emission and Information Encryption

AbstractTwo dumbbell‐shaped building blocks (TMB and TMBT), featuring methyl benzoate groups as hydrogen bond units, are selected to construct heterostructures of HOFs, aiming to achieve multiple functions including white luminescence, stimulus‐response behavior, as well as application in information encryption. TMB molecules are self‐assembled to form a flexible HOF (X‐HOF‐8) in p‐xylene, containing solvent channels and blue fluorescence. Upon removal of guests, it can transform into a nonporous crystal with gray fluorescence. In contrast, TMBT forms a guest‐free HOF (X‐HOF‐9) displaying orange fluorescence. They could form bulk heterojunction (BHJ) HOFs with energy transfer from TMB to TMBT, exhibiting composition‐dependent fluorescent color. Notably, white emission can be achieved in BHJ HOFs and can be converted to gray fluorescence upon guest removal; subsequently, white fluorescence is restored upon re‐capturing guests. Furthermore, rod‐like triblock heterojunction (THJ) HOFs can also be constructed, which exhibit regulatory behavior in response to gaining or losing guests. The unique luminescent characteristics and stimulus responsiveness of these HOFs make them an excellent platform for applications in anticounterfeit. This represents the pioneering achievement of white light emission in a BHJ HOF, as well as the groundbreaking realization of a THJ HOF with remarkable exciting response characteristics.

Rapid and Efficient Dual Detection Of Zn2+ Ions and Oxytetracycline Hydrochloride Using a Responsive Fluorescent "On-Off" Sensor Based on Simple Salen-Type Schiff Base Ligand.

This research has progressed to an effective detection chemosensor of zinc, aluminum ions and oxytetracycline hydrochloride antibiotic based on the fluorescence technique. A straightforward method utilizing microwave irradiation was employed to synthesize the salen-type Schiff base ligand N,N'-bis(salicylaldehyde)4,5-dichloro-1,2-phenylenediamine (H2I), providing a good 70 % yield. In ethanol, the H2I sensor demonstrated remarkable rapidity, selectivity, and sensitivity in detecting zinc ions. The fluorescence spectrum exhibited a 44-fold substantial enhancement at 522 nm and achieved a low limit of detection (LOD) of 1.47 μM. Furthermore, the H2I probe's emission intensity increased by 124 times when compared to the ligand's ability to detect Al3+ ions at 494 nm with a LOD value of 7.4 μM. Additional research was done using the H2I probe's effective Zn2+ detection capability. The ability to recognize zinc ions in different real water samples demonstrated a recovery rate of 98.67 % to 103.31 %. Interestingly, a naked-eye visible fluorescence color of H2I solution impregnated filter papers turned colorless into yell ow under UV irradiation by adding Zn2+ ions, renders it suitable for developing a practical zinc ion detection kit test. In particular, the I-Zn2+ complex effectively quenched the fluorescence toward oxytetracycline hydrochloride (OTC) with a LOD value of 1.49×10-2 μM in DMSO:H2O (6 : 4, v/v). This is a novel and effective procedure for sensing OTC antibiotic by the I-Zn2+ complex. These findings hold immense potential for the development of dual fluorescent probes, thereby enhancing sensitivity and specificity in identifying metal ions and antibiotics in a wide range of applications.

Self‐assembled small molecule spherulites under mild conditions: High solid‐state quantum yield and unique interconnected structural and fluorescent colors

AbstractSpherulites are generally fabricated from cooling polymer melts, while their fabrication under mild conditions or from small molecule materials has been barely reported. Besides, organic luminescent molecules typically suffer from low quantum yields in a solid state. Moreover, preparing material with interconnected and simultaneous changes in structural and fluorescent colors is challenging. Here, we present the first solution‐derived spherulites with unique interconnected structural and fluorescent colors, self‐assembled from stearoylated monosaccharides at room temperature. D‐galactose stearoyl ester self‐assembled into banded spherulites, containing twisted nanoplates and interconnected simultaneously changing structural and fluorescent colors. In comparison, D‐mannose stearoyl ester can only form non‐banded spherulites, which contain oriented nanoplates and uniform structural and fluorescent colors. Such materials revealed a novel negative correlation between fluorescence and birefringence, termed alignment‐promoted quenching propensity. Remarkably, the solid‐state fluorescence quantum yields of galactose and mannose‐derived spherulites are as high as 49 ± 2% and 51 ± 2% respectively, approximately ten times higher than those of unmodified monosaccharides. These quantum yield values are among the highest of reported organic nonconventional fluorophores and even comparable to those of conventional aromatic chromophores. Moreover, these spherulites manifested an unexpected excitation‐dependent multicolor photoluminescence with a broad‐spectrum emission (410−620 nm). They show multiple peaks in the photoluminescent emission spectra and broad fluorescence lifetime distributions, which should be attributed to the clustering of a variety of oxygen‐containing functional groups as emissive moieties.

Dual-mode sensing platform for Bisphenol A detection via bifunctional CsPbBr3@Cu-MOF assisted fluorescence and colorimetric analysis

BackgroundBisphenol A (BPA) has been identified as an endocrine disruptor with numerous detrimental effects on human health. There is an urgent need to develop fluorescence/colorimetric dual-mode sensing approaches with expanded detection linear range, increased accuracy, and enhanced application flexibility for BPA detection. The utilization of fluorescence and colorimetric signals in point-of-care applications and real-time sensitive sensing further highlights the significance of developing novel and efficient fluorescence/colorimetric dual-mode sensing platform with high-efficiency probes. ResultsHerein, a fluorescence and colorimetric dual-mode aptasensor was developed by using CsPbBr3@Cu-MOF as the aptamer immobilization matrix and signal generator. CsPbBr3 was functionalized with Cu-MOF using a simple two-step strategy. This strategy involved in-situ formation and modified ligand-assisted precipitation technique with 4,4′-bipyridine (4,4-Bpy) serving as the bifunctional linker. The resulting CsPbBr3@Cu-MOF exhibited improved stability in water and enhanced fluorescence. Additionally, it functioned as peroxidase mimetic to oxidize 3,3′,5,5′-tetramethyl benzidine (TMB), leading to a colorimetric change from colorless to blue. In the presence of BPA, aptamers were removed from CsPbBr3@Cu-MOF. Consequently, the fluorescence and peroxidase-activity of CsPbBr3@Cu-MOF were recovered, resulting in the enhanced fluorescence intensity and color change of TMB. Using this system, the proposed aptasensor demonstrated detection ranges of 1.0–80.0 nM with a LOD of 0.60 nM for the colorimetric method, and a linearity range of 0.1–100 nM with a LOD of 0.02 nM for the fluorescence method. SignificanceThe obtained CsPbBr3@Cu-MOF composites showed excellent fluorescence properties, good peroxidase-like activity, and aqueous stability. Furthermore, the proposed dual-mode aptasensor demonstrated simplicity, cost-effectiveness and good anti-interference abilities. This can be extended to the construction of other dual-mode sensors by changing aptamers and provides novel insights on the potential applications of perovskites in bioanalysis.

Ultrabright silicon nanoparticles combined with o-phenylenediamine for ratiometric fluorescence and smartphone imaging dual-mode detection of nitrite

Nitrite (NO2−) is widely present in the natural environment and human daily life. Excessive NO2− can cause harm to the environment and human health. Herein, silicon nanoparticles (SiNPs) with a fluorescence quantum yield of up to 70 % were synthesised using a one-pot hydrothermal method and combined with the common and inexpensive o-phenylenediamine (OPD) to achieve the detection of NO2−. Upon the addition of NO2−, the blue fluorescence of the SiNPs was quenched due to static quenching and Förster resonance energy transfer (FRET), while the yellow fluorescence of benzotriazole, the reaction product of OPD and NO2−, was enhanced, resulting in the fluorescence color change from blue to yellow. Based on these phenomena, a ratiometric fluorescence sensor integrated with smartphone imaging technology was developed. This sensor is notable for its portability, cost-effectiveness, and satisfactory detection limits (0.016 μM for ratiometric fluorescence and 1.64 μM for smartphone imaging). Importantly, it demonstrates high reliability and practicability in detecting NO2− in real water and food samples. This broadens the application of SiNPs in the sensing field and introduces new possibilities for NO2− detection in complex sample matrices.

Concentration dependent carbon nanodots: Tunable luminescent color and fluorescence excitation-wavelength dependence

Carbon nanodots (CNDs) exhibiting concentration dependent properties have been synthesized through a one-pot hydrothermal reaction process utilizing diethylenetriamine and l-aspartic acid. At solid-state or high concentrations, the CNDs display excitation-wavelength independent fluorescence (FL) emissions, while at low concentrations, they exhibit excitation-wavelength dependent FL emissions. Detailed characterization of the structure and optical properties reveals that the concentration dependent FL properties can be ascribed to the intrinsic-state luminescence of the CNDs at low concentrations and the assembled-state luminescence at solid-state/high concentrations. With the increase of concentration, the self-assembly behavior of CNDs may cause the transition from intrinsic-state dominant luminescence to assembled-state dominant luminescence, and finally lead to the red-shift of FL color. Furthermore, the CNDs@Urea composites possess adjustable room-temperature phosphorescence (RTP) from turquoise to yellow by controlling the CNDs doping concentration. CNDs with concentration dependent optical properties have shown certain potentials in the fields of cell imaging, fingerprint recognition and anti-counterfeiting applications.

Intramolecular Charge Transfer Inhibition Strategy toward a Desired Solvatochromic Fluorescent Platform: Visualization of Duple Organelles and Detection of Carbon Dioxide.

Solvatochromic fluorescent probes are crucial molecular tools to investigate and aggregate proteins' fold, visualize fine structures in biomembranes, and label different organelles in dual emission colors. However, solvatochromic fluorogens often displayed a weak emission at high polarity, hindering their bioimaging applications. To resolve this problem, herein, we propose an intramolecular charge transfer (ICT) inhibition strategy. The probe was designed with a single electronic donor and two acceptors in order to split and inhibit the ICT procedure. As a result, the probe displayed an intense emission at both low and high polarities and showed a large emission shift (84 nm) upon polarity change. Using the probe, we successfully imaged lipid droplets and the endoplasmic reticulum in different fluorescence colors. Moreover, the different degrees of lipid accumulation by oleic acid, stearic acid, and cholesterol (oleic acid > stearic acid > cholesterol) have been revealed. The lipid accumulation induced by the three lipids could be rapidly consumed under lipid-less conditions, and the lipids with stearic acid were the most difficult to be consumed. The biological results could facilitate the understanding and treatment of lipid accumulation and obesity. Furthermore, utilizing the polarity increase of diethylamine after the reaction with CO2, the ratiometric detection of CO2 has been achieved for the first time with the probe.

Rational Design of Regenerable Amino-Functionalized Fluorescent Covalent Organic Framework for the Exclusive Detection of Mercury(II).

Goal-oriented development of novel covalent organic frameworks (COFs) to construct a sensing platform for highly toxic mercury (II, Hg2+) is of tremendous significance. Recently, numerous COFs with sulfur-based ligands were developed for Hg2+ monitoring; however, strong binding of Hg2+ by sulfur makes their regeneration very tough. Herein, we designed and developed an amino-functionalized fluorescent COF (COF-NH2) through facile postmodification for Hg2+ detection in which the π-conjugation skeleton is the signal reader and the nitrogen-based side is the highly selective Hg2+ receptor. More importantly, this nitrogen-based receptor permits the reversible binding of Hg2+. As a sensing platform, the outstanding performance of COF-NH2 for Hg2+ detection was reached with respect to high sensitivity with an ultralow detection of 15.3 nM, real-time response with rapid signal change of 10 s, and facile visualization with significant fluorescence color change. Expectedly, COF-NH2 obtained facile recycling which still shows excellent response performance toward Hg2+ after six cycles based on the reversible interaction between amino groups and Hg2+. Our work not only shows an attractive foreground of fluorescent COF for Hg2+ detection but also emphasizes the easy construction of novel COF materials via the rational introduction of metal ligands for the recognition of other metal ions.

Unlocking the Luminescent Potential of Fish-Scale-Derived Carbon Nanoparticles for Multicolor Conversion.

This study introduces a novel approach to addressing environmental issues by developing fish-scale carbon nanoparticles (FSCNPs) with a wide range of colors from discarded fish scales. The process involves hydrothermally synthesizing raw tamban (Sardinella) fish scales sourced from Universal Canning, Inc. in Zamboanga City, Philippines. The optimization of the synthesis was achieved using the response surface methodology with a Box-Behnken design. The resulting FSCNPs exhibited unique structural and chemical properties akin to carbonized polymer dots, enhancing their versatility. The solid-state fluorescence of these nanoparticles can be modulated by varying their concentration in a polyvinylpyrrolidone matrix, yielding colors such as blue, green, yellow, and red-orange with Commission Internationale de l'Eclairage coordinates of (0.23, 0.38), (0.32, 0.43), (0.37, 0.43), and (0.46, 0.48), respectively. An analysis of the luminescence mechanism highlights cross-linking emissions, aggregation-induced emissions, and non-covalent interactions, which contribute to concentration-dependent fluorescence and tunable emission colors. These optical characteristics suggest that FSCNPs have significant potential for diverse applications, particularly in opto-electronic devices.

Fusion of visible and fluorescence imaging through deep neural network for color value prediction of pelletized red peppers.

A non-destructive method for determining the color value of pelletized red peppers is crucial for pepper processing factories. This study aimed to investigate the potentiality of visible and fluorescence images for the determination of color value of pelletized red pepper. The imaging problem, caused by the cylindrical shape and irregular cross-sectional features of the pelletized red peppers, was reduced through the extraction of an approximate plane region. To integrate the information in the visible and fluorescence images, a baseline convolutional neural network (CNN) architecture was designed and low level, middle level, and high level fusion models (denoted as LL-CNN, ML-CNN, and HL-CNN, respectively) were developed upon the baseline CNN. The effects of input image size and color space were examined. According to the training result, CNN fusion models were developed using visible image in L*a*b* color space and fluorescence image in RGB color space using 56×56 input image size. Among the three types of CNN fusion models, the HL-CNN obtained the best performance, resulting in Rv 2 of 0.828 and RMSEV of 0.351. This study suggests that the fusion of visible and fluorescence image through CNN is a practical approach to save testing time and replace traditional destructive method. The low cost and compact structure of the imaging systems can maintain the commercial appeal of pepper industry.

Multifunctional Au–Ag NCs for luminescence and colorimetric double signal sensing of H2S and catalytic reduction of nitrophenol

In this study, the N-Acetyl-l-Cysteine (NAC)-capped gold and silver bimetallic nanoclusters (NAC@Au–Ag NCs) was synthesized by reflux method. Due to the silver effect, the NAC@Au–Ag NCs exhibited strong photoluminescence at far-red/near-infrared regions and better catalytic performance than Au or Ag NCs. Upon addition of H2S, the Au–Ag NCs exhibited obvious fluorescence quench and color changes through the generation of metal sulfides and a static quenching process. The Au–Ag NCs displayed a wide linear luminescence response for H2S (18.5–217 μmol/L) with a detection limit of 0.269 μmol/L. Moreover, the visible color of Au–Ag NCs changed from white to brown-yellow along with increased H2S, the corresponding RGB values also displayed good linearity with the concentration of H2S (90.1–678 μmol/L). Notably, the fabrication of test strips provided a convenient and intuitive tool to screen the freshness of eggs by the color change of test strips. Au–Ag NCs could be used for living HeLa cells bioimaging and recognition of H2S abnormalities. Furthermore, it can be used as a catalyst to reduction of nitrophenols (NPhs), specific included 2NP, 3NP and 4NP. The reaction was regarded as a pseudo-first-order kinetic reaction due to the presence of excess NaBH4. At 298K, the catalytic rate constants(k) of 2NP, 3NP and 4NP were 0.1754 min−1, 0.1734 min−1 and 0.2782 min−1, respectively. The NAC@Au–Ag NCs catalyst still showed good catalytic activity and reusability after five cycles. Therefore, this study developed a H2S sensor for food samples and biological systems. And this nanocatalyst had great application potential for removed the nitrophenol pollutants in water.

Stimuli-Induced Fluorescence Switching in Azine-Containing Fluorophores Displaying Resonance-Stabilized ESIPT Emission.

This article reports the synthesis, along with structural and photophysical characterization of 2-(2'-hydroxyphenyl)benzazole derivatives functionalized with various azaheterocycles (pyridine, pyrimidine, terpyridine). These compounds show dual-state emission properties, that is intense fluorescence both in solution and in the solid-state with a range of fluorescent color going from blue to orange. Moreover, the nature of their excited state can be tuned by the presence of external stimuli such as protons or metal cations. In the absence of stimuli, these dyes show emission stemming from anionic species obtained after deprotonation (D* transition), whereas upon protonation or metal chelation, ESIPT process occurs leading to a stabilized and highly emissive K* transition. With the help of extensive ab initio calculations, we confirm that external stimuli can switch the nature of the transitions, making this series of dyes attractive candidates for the development of stimuli-responsive fluorescent ratiometric probes.

An Aggregation-Induced Emissive Platinum(II) Metallacycle as the Energy Donor of Rhodols for Ratiometric Detection of Hydrazine.

Industry-produced hydrazine (N2H4) is released into the environment, posing a major risk to human health and the ecosystem. Therefore, it is imperative to develop an effective and convenient method for the detection of N2H4. Herein, artificial light-harvesting systems (ALHSs) for N2H4 detection were constructed by applying an aggregation-induced emission-active platinum(II) metallacycle (TPEMc) as the energy donor and rhodols (P1, P2, and P3) as the energy acceptors. The ratiometric fluorescence probes based on ALHSs for N2H4 showed obvious signal amplification and lower limits of detection compared to those of rhodols (P1, P2, P3) alone. The TPEMc-rhodols systems clearly demonstrated a noticeable increase in fluorescence intensity at 550 nm and an obvious fluorescent color shift from cyan to yellow in the presence of N2H4. Fascinatingly, N2H4 could be visually and quantitatively detected in water by the TPEMc-rhodol systems paired with smartphone RGB analysis. Therefore, the combination of platinum(II) metallacycle with rhodols is a promising strategy for simple, sensitive, and visual detection of N2H4.

A Carbazole-based Fluorescent Probe with AIE Performance and a Large Stokes Shift for Peroxynitrite Detection and Imaging in Live Cells.

A carbazole-based fluorescent probe YCN with AIE performance and a large Stokes shift (242nm) shift was synthesized by attaching 4-acetonitrile pyridine to the 3-phenylaldehyde butylcarbazole. Its structure was characterized by 1H NMR, 13C NMR and MS. Probe YCN has high selectivity and sensitivity toward ONOO-. The addition of ONOO- to the probe YCN solution results in a noticeable color change from pale yellow to colorless under natural light, and a fluorescent color change from bright orange-yellow to bright yellow-green under a 365nm UV lamp, which can be distinguished by the naked eye. The research results on the reaction mechanism showed that when YCN reacted with ONOO-, -C = C- was oxidized and broken into -CHO, and the ICT effect was significantly inhibited, resulting in changes in UV absorption and fluorescence emission phenomenon. The recognition mechanism was verified by 1H NMR, mass spectrometry (MS) and density function theory (DFT) calculations. The experiments of live cells imaging suggested that compound YCN can be used as a fluorescent probe for the detection of ONOO- in HeLa cells. This result indicates that YCN has potential application prospects in the biological aspects.

Nanozyme-mediated ratiometric fluorescence hydrogel for on-site detection of sulfite in food

In this work, a ratiometric fluorescence hydrogel nanosensor was developed by integrating a composite consisting of o-phenylenediamine (OPD), manganese dioxide nanoflakes (MnO2 NFs), and N-doped carbon dots (N-CDs) into an agarose hydrogel for sulfite detection. MnO2 NFs demonstrated intense oxidase-like activity, facilitating the conversion of non-fluorescent OPD into yellow-emissive 2,3-diaminophenazine (DAP). As a result, a significant emission peak belongs to DAP, alongside the fluorescence quenching of N-CDs through FRET. Upon interaction with sulfite, MnO2 NFs lost their oxidase-like function. This process decreased the fluorescence of DAP and restored the blue fluorescence of N-CDs, producing a typical ratiometric response, ranging from 3 nM ∼ 400 μM, with a detection limit (LOD) of 3.79 nM. Employing a smartphone, the fluorescence color change demonstrated by the hydrogel sensor was translated into quantitative data (LOD: 8.44 nM). This hydrogel sensor offers an affordable, portable, and user-friendly solution for sulfite detection and food safety monitoring.

Acne-related UVA-induced facial fluorescence: An exploratory study from physiological properties to tissue structure information

UVA-induced facial fluorescence (UVAF) is recognized as an objective measurement technique to quantify the severity of acne. However, notable inconsistencies in quantitative outcomes have been observed in various studies, possibly due to the fact that different colors of fluorescence represent different pathophysiological implications. This study investigated the pathophysiological importance of UVAF color differences and improved its reliability in assessing acne severity. MIDOO Smart Skin Imager was used to capture UVAF and analyze the correlation between fluorescence colors and acne lesions. Techniques such as two-photon excited fluorescence microscopy, scanning electron microscopy, western blot, and high performance liquid chromatography-mass spectrometry (HPLC-MS/MS) were used to examine the biochemical composition and structure of comedonal plugs and follicular casts associated with different fluorescence colors. We found that green fluorescence correlates with non-inflammatory acne lesions (comedones), while orange-red fluorescence shows no correlation with either type of lesion. Green fluorescence is associated with higher levels of keratin, indicating keratinization, while orange-red fluorescence is associated with porphyrin from S. epidermidis. UVAF color differences - orange-red are from porphyrins and green from keratin. This distinction helps to understand the structural and physiological bases of facial fluorescence, with potential implications for clinical evaluations of acne.

The Solid-State Multi-Color Fluorescence Switching from a [2.2]Paracyclophane-Based Triarylborane.

The fluorophores, the fluorescence of which can be switched between multi bright colors in the solid state, show promising applications not only in the sophisticated multicolor display but also in the advanced encryption and anti-counterfeiting systems. However, it is very challenging to obtain such fluorophores. Herein, we disclose such an example, g-BPhANMe2-Cp, which contains an electron-donating dimethylamino (NMe2) and an electron-accepting [(2-dimesitylboryl)phenyl]acetyl at the pseudo-gem position of [2.2]paracyclophane skeleton. This molecule can display tricolor mechanochromic luminescence (MCL) due to the different responses of the mechanically ground amorphous state to heating and solvent-fuming. Owing to the absence of intermolecular π-π interactions in the solid state, the fluorescence efficiency is very high irrespective of its morphological state (ΦF=0.60-0.87). Moreover, this molecule also displays reversible acidochromic luminescence (ACL) by protonation and deprotonation of NMe2 with trifluoroacetic acid (TFA) and triethylamine (TEA), respectively. The protonated sample fluoresces (ΦF=0.31) at much shorter wavelength due to the interruption of intramolecular charge transfer process. Therefore, with the combination of tricolor MCL and ACL properties, the solid-state emission of g-BPhANMe2-Cp can be switched among four bright fluorescence colors of yellow, green, cyan and blue via treatment with appropriate stimulus.

Expanding the Color Range of Photoresponsive Multicolor Luminescent System Through Host-Guest Interaction.

Photoresponsive multicolor luminescent systems offer interesting functions, which have led to applications in anticounterfeiting and biological imaging. However, expanding the color range of these materials remains a challenging task. Herein, a carbazole-modified dithienylethene derivative (DTE-CZ) that exhibits modulated fluorescence color changes through the photocyclization reaction and photolysis reaction is synthesized. DTE-CZ emits orange fluorescence, and it can release a fluorophore which emits blue fluorescence by the photolysis reaction, resulting in the color change. Upon complexation of DTE-CZ with cucurbit[10]uril (CB[10]), the fluorescence wavelength will have a blue shift and the photolysis reaction will be inhibited. Benefiting from the influence of CB[10] and the photolysis reaction of free guests, the color range of the photoresponsive system which is composed of free guests and host-guest complexes is further extended. White light emission along with a color shift from yellow-green to blue was achieved by adjusting the ratio of free guests to host-guest complexes. Finally, the photoresponsive multicolor systems are utilized to construct a photostimulated PVA film and an information encryption system. This work provides an alternative strategy for the preparing of photoresponsive multicolor luminescent system and modulation of its color range.