Electropolymerization of Preferred-Oriented Conjugated Microporous Polymer Films for Enhanced Fluorescent Sensing.

High-quality conjugated microporous polymer (CMP) films with orientation and controlled structure are extremely desired for applications. Here, we report the effective construction of CMP 3D composite films (pZn/PTPCz) with a controlled porosity structure and preferred orientation using the template-assisted electropolymerization (EP) approach for the first time. The structure of pZn/PTPCz composite thin films and nitrophenol sensing performance were thoroughly studied. When compared to the control CMP film made on flat indium tin oxide (ITO) substrates, the as-prepared pZn/PTPCz composite films showed significantly enhanced fluorescent intensity and much better sensing performance for the model explosive. This was attributed to the metal-enhanced fluorescence (MEF) of porous nanostructured zinc (pZn) and the additional macroporosity of the pZn/PTPCz composite films. This work provides a feasible approach for creating oriented 3D CMP-based thin films for advanced applications.

Enabling Highly Robust Full-Color Ultralong Room-Temperature Phosphorescence and Stable White Organic Afterglow from Polycyclic Aromatic Hydrocarbons.

In this work, full-color and stable white organic afterglow materials with outstanding water, organic solvents, and temperature resistances have been developed for the first time by embedding the selected polycyclic aromatic hydrocarbons into melamine-formaldehyde polymer via solution polymerization. The afterglow quantum yields and lifetimes of the resulting polymer films were up to 22.7 % and 4.83 s, respectively, under ambient conditions. For the coronene-doped sample, its afterglow color could be linearly tuned between yellow and blue by adjusting the temperature, and it could still emit an intense blue afterglow with a lifetime of 0.68 s at 440 K. Moreover, the films showed a bright and stable white afterglow at 370 K with a lifetime of 2.80 s and maintained an excellent afterglow performance after soaking in water and organic solvents for more than 150 days. In addition, the application potential of the polymer films in information encryption and anti-counterfeiting was also demonstrated.

Bright Organic Mechanoluminescence and Remarkable Mechanofluorochromism from Circularly Polarized TADF Enantiomers with Aggregation-Induced Emission Properties.

The development of circularly polarized thermally activated delayed fluorescence (CP-TADF) luminogens with stimuli-response characteristics remains challenging. Herein, a pair of organic enantiomers, S-CzTA and R-CzTA, with aggregation-induced emission properties, have been successfully developed by introducing chiral 1,2,3,4-tetrahydronaphthalene and carbazole to phthalimide. They present CP-TADF properties in toluene solutions, giving dissymmetric factors of 0.84×10-3 and -1.03×10-3 , respectively. In the crystalline state, both S-CzTA and R-CzTA can emit intense blue TADF and produce very bright sky-blue mechanoluminescence (ML) and remarkable mechanofluorochromism (MFC) under the stimuli of mechanical force. Single-crystal analysis and theoretical calculation results suggest that their ML activities are probably associated with their chiral and polar molecular structures and unique non-centrosymmetric molecular packing modes. Furthermore, the MFC properties of the enantiomers likely originate from the destruction of crystal structure, leading to the planarization of molecular conformation. This work may provide helpful guidance for developing new CP-TADF materials with force-stimuli-responsive properties.

Reblooming of the cis-Bis(2-phenylpyridine) Platinum(II) Complex: Synthesis Updating, Aggregation-Induced Emission, Electroluminescence, and Cell Imaging.

Studies on the syntheses, photophysical properties, and applications of cis-bis(2-phenylpyridine) platinum(II) complex (Pt(ppy)2) family are of great importance, but very limited progress has been achieved to date. Herein, a one-pot method was established for the syntheses of Pt(ppy)2-type complexes Pt-ppy and Pt-tBu. These two compounds were nonemissive in dilute solutions. However, they produced intense red and deep-red phosphorescence in the aggregation and film states, with lifetimes and quantum yields up to 1.92 µs and 70%, respectively, exhibiting unique aggregation-induced emission (AIE) characteristics. According to the experimental and theoretical studies, molecular configuration transformation (MCT) in the excited state may occur because of the d-d transition from the Pt center, causing nonradiative transitions in the solution. Nevertheless, the MCT would be largely restricted by the intermolecular interactions or rigid matrix, thereby enabling efficient phosphorescence in the aggregation state and in the PMMA films. Consequently, the AIE characteristics of Pt-ppy and Pt-tBu probably result from the restriction of molecular configuration transformation (RMCT). Due to the π-π and/or weak Pt-Pt interactions and the concentration-dependent emission characteristics, they emit deep-red and NIR emissions generated by excimer and/or MMLCT emitting species. Inspired by their AIE features, electroluminescence and cell imaging applications are explored. To the best of our knowledge, this is the first comprehensive study on the synthesis optimization, photophysical properties, AIE characteristics, and applications of the Pt(ppy)2-type complexes, which may rebloom the research studies on this type of Pt(II) complex family and provide valuable insights on the development of phosphorescent AIE metal-organic complexes.

Switchable and Highly Robust Ultralong Room-Temperature Phosphorescence from Polymer-Based Transparent Films with Three-Dimensional Covalent Networks for Erasable Light Printing.

In this work, an efficient polymer-based organic afterglow system, which shows reversible photochromism, switchable ultralong organic phosphorescence (UOP), and prominent water and chemical resistance simultaneously, has been developed for the first time. By doping phenoxazine (PXZ) and 10-ethyl-10H-phenoxazine (PXZEt) into epoxy polymers, the resulting PXZ@EP-0.25 % and PXZEt@EP-0.25 % films show unique photoactivated UOP properties, with phosphorescence quantum yields and lifetimes up to 10.8 % and 845 ms, respectively. It is found that the steady-state luminescence and UOP of PXZ@EP-0.25 % are switchable by light irradiation and thermal annealing. Moreover, the doped films can still produce conspicuous UOP after soaking in water, strong acid and base, and organic solvents for more than two weeks, exhibiting outstanding water and chemical resistance. Inspired by these exciting results, the PXZ@EP-0.25 % has been successfully exploited as an erasable transparent film for light printing.

Color-Tunable Dual-Mode Organic Afterglow from Classical Aggregation-Caused Quenching Compounds for White-Light-Manipulated Anti-Counterfeiting.

Color-tunable dual-mode organic afterglow excited by ultraviolet (UV) and white light was achieved from classical aggregation-caused quenching compounds for the first time. Specifically, two luminescent systems, which could produce significant organic afterglow composed of persistent thermally activated delayed fluorescence and ultralong organic phosphorescence under ambient conditions, were constructed by doping fluorescein sodium and calcein sodium into aluminum sulfate. Their lifetimes surpassed 600 ms, and the dopant concentrations were as low as 5×10-6  wt %. Moreover, the persistent luminescence colors of the materials could be tuned from blue to green and then to yellow by simply varying the concentrations of guest compounds or the temperature in the range of 260-340 K. Inspired by these exciting results, the afterglow materials were used for UV- and white-light-manipulated anti-counterfeiting and preparation of elastomers with different colors of persistent luminescence.

Efficient and Color-Tunable Dual-Mode Afterglow from Large-Area and Flexible Polymer-Based Transparent Films for Anti-Counterfeiting and Information Encryption.

It remains a great challenge to develop polymer-based materials with efficient and color-tunable organic afterglow. Two indolocarbazole derivatives IaCzA and IbCzA have been synthesized and doped into poly(vinyl alcohol) (PVA) matrices. It is found that the resulting films can produce unique dual-mode afterglow, which is composed of persistent thermally activated delayed fluorescence and ultralong organic phosphorescence. Besides, the IbCzA-doped PVA film exhibits intense blue afterglow with Φafterglow and τafterglow up to 19.8 % and 1.81 s, respectively, representing state-of-the-art dual-mode organic afterglow performance. Moreover, our reported film has high flexibility, excellent transparency, and large-area producibility; and the afterglow color of the film can be linearly tuned by temperature. Inspired by these distinctive properties, the PVA doped with IbCzA was employed as temperature-sensitive security ink for anti-counterfeiting and information encryption.

Transient and Persistent Room-Temperature Mechanoluminescence from a White-Light-Emitting AIEgen with Tricolor Emission Switching Triggered by Light.

Persistent luminescence from purely organic materials is basically triggered by light and electricity, which largely confines its practical applications. A purely organic AIEgen exhibits not only persistent photoluminescence, but also transient and persistent room-temperature mechanoluminescence. By simply turning on and off a UV lamp, tricolor emission switching between blue, white, and yellow was achieved. The data from single-crystal structure analysis and theoretical calculation suggest that mechanism of the observed persistent mechanoluminescence (pML) is correlated with the strong spin-orbit coupling of the bromine atom, as well as the formation of H-aggregates and restriction of intramolecular motions in noncentrosymmetric crystal structure. These results outline a fundamental principle for the development of new pML materials, providing an important step forward in expanding the application scope of persistent luminescence.

Recent advances in organic mechanofluorochromic materials.

Mechanofluorochromic materials, which are dependent on changes in physical molecular packing modes, have attracted considerable interest over the past ten years. In this review, recent progress in the area of pure organic mechanofluorochromism is summarized, and majority of the reported organic mechanofluorochromic systems are discussed, along with their derived structure-property relationships. The existence of a structural relationship between aggregation-induced emission compounds and mechanofluorochromism is recognized based on our recent results, which considered aggregation-induced emission compounds as a well of mechanofluorochromic materials. The established structure-property relationship will guide researchers in identifying and synthesizing more mechanofluorochromic materials.

Construction and Application of Large Stokes-Shift Organic Room Temperature Phosphorescence Materials by Intermolecular Charge Transfer.

Notably, the intermolecular charge transfer between pyrene (Py) and benzophonenes (BPs) can significantly enhance the quantum yield of the triplet state of Py, which will convert Py from a fluorescence molecule to a phosphorescence molecule. The intermolecular charge transfer is confirmed by steady-state and time-resolved spectroscopy and theoretical study. Based on these foundations, Py is doped into BPs systems and a large Stokes-shift organic room temperature phosphorescence (ORTP) is observed. By using different benzophenone derivatives, a series of host-guest ORTP materials with different luminescent properties adjusted by intermolecular charge transfer features are developed. Fortunately, these host-guest ORTP systems from benzophenone derivatives and pyrene are readily fabricated, and the red gradient color lasting as long as 3 s is observed after removing UV excitation. This host-guest charge transfer strategy plays an important role in the mechanism of the luminous type shift. Our strategy paves the way to design ORTP materials conveniently and apply these materials in encryption and temperature alarm device.

Polymer-Based Long-Lived Phosphorescence Materials over a Broad Temperature Based on Coumarin Derivatives as Information Anti-Counterfeiting.

The development of new polymer-based room-temperature phosphorescence materials is of great significance. By a special molecule design and a set of feasible property-enhancing strategies, coumarin derivatives (CMDs, Ma-Mf) were doped into polyvinyl alcohol (PVA), polyacrylamide (PAM), corn starch, and polyacrylonitrile (PAN) as information anti-counterfeiting. CMDs-doped PVA and CMDs-doped corn starch films showed long-lived phosphorescence emissions up to 1246 ms (Ma-PVA) and 697 ms (Ma-corn starch), reaching over 10 s afterglow under naked eye observation under ambient conditions. Significantly, CMDs-doped PAM films can display long-lived phosphorescence emissions in a wide temperature range (100-430 K). For example, the Me-PAM film has a phosphorescence lifetime of 16 ms at 430 K. The use of PAM with the strong polarity and rigidity has expanded the temperature range of long-life polymer-based phosphorescent materials. The present long-lived phosphorescent systems provide the possibility for developing new polymer-based organic afterglow materials with robust phosphorescence.

Fine-tuning benzazole-based probe for the ultrasensitive detection of Hg2+ in water samples and seaweed samples.

Developing potentially toxic metal ion probes is significant for environment and food safety. Although Hg2+ probes have been extensively studied, small molecule fluorophores that can integrate two applications of visual detection and separation into one unit remain challenging to access. Herein, by incorporating triphenylamine (TPA) into tridentate skeleton with an acetylene bridge, 2,6-bisbenzimidazolpyridine-TPA (4a), 2,6-bisbenzothiazolylpyridine-TPA (4b) and 2,6-bisbenzothiazolylpyridine-TPA (4c) were first constructed, expectably showing distinct solvatochromism and dual-state emission properties. Since the diverse emission properties, the fluorescence detection of 4a-4b can be achieved with an ultrasensitive response (LOD = 10-11 M) and efficient removal of Hg2+. More interestingly, 4a-4b can not only be developed into paper/film sensing platform, but also reliably detect Hg2+ in real water and seaweed samples, with recoveries ranging from 97.3% to 107.8% and a relative standard deviation of less than 5%, indicating that they have excellent application potential in the field of environmental and food chemistry.

Achieving Stable and Switchable Ultralong Room-Temperature Phosphorescence from Polymer-Based Luminescent Materials with Three-Dimensional Covalent Networks for Light-Manipulated Anticounterfeiting.

Developing polymer-based organic afterglow materials with switchable ultralong organic phosphorescence (UOP) that are insensitive to moisture remains challenging. Herein, two organic luminogens, BBCC and BBCS, were synthesized by attaching 7H-benzo[c]carbazole (BBC) to benzophenone and diphenyl sulfone. These two emitters were employed as guest molecules and doped into epoxy polymers (EPs), which were constructed by in situ polymerization to achieve polymer materials BBCC-EP and BBCS-EP. It was found that BBCC-EP and BBCS-EP films exhibited significant photoactivated UOP properties. After light irradiation, they could produce a conspicuous organic afterglow with phosphorescence quantum yields and lifetimes up to 5.35% and 1.91 s, respectively. Meanwhile, BBCS-EP also presented photochromic characteristics. Upon thermal annealing, the UOP could be turned off, and the polymer films recovered to their pristine state, showing switchable organic afterglow. In addition, BBCC-EP and BBCS-EP displayed excellent water resistance and still produced obvious UOP after soaking in water for 4 weeks. Inspired by the unique photoactivated UOP and photochromic properties, BBCC and BBCS in the mixtures of diglycidyl ether of bisphenol A (DGEBA) and 1,3-propanediamine were employed as security inks for light-controlled multilevel anticounterfeiting. This work may provide helpful guidance for developing photostimuli-responsive polymer-based organic afterglow materials, especially those with stable UOP under ambient conditions.

A new piezochromic fluorescence and aggregation-induced emission compound containing tetraphenylethylene and triphenylamine moieties with morphology-alterable property.

A novel piezochromic fluorescent (PCF) compound with aggregation-induced emission (AIE) effect and morphology-alterable emission property was developed. The amorphous and crystalline aggregates were obtained, and their spectroscopic properties and morphological structures were reversibly and repeatedly exhibited upon pressing (fuming) or annealing. The piezochromic fluorescent nature was generated through crystalline-amorphous phase transformation. It was proposed that AIE compounds existing a twisted propeller-shaped conformation will exhibit PCF activity. The common relationship betweeen AIE and PCF established will guide researchers in identifying and synthesizing more piezochromic fluorescent materials.

Comparison of responsive behaviors of two cinnamic acid derivatives containing carbazolyl triphenylethylene.

Two cinnamic acid derivatives (CPA and CPC) containing carbazolyl triphenylethylene moiety have been synthesized and characterized. The two derivatives possessed aggregation-induced emission property. They exhibited different and interesting responsive behaviors to solvents, water and metal ions. Considering the structural differences between the two derivatives resulting in different interactions between their molecules and the various media was proposed as a possible explanation for these observations. The intermolecular interactions of CPC were much stronger than those of CPA, which promoted molecular association through intermolecular hydrogen bonding to form multimers. It was found that CPC and CPA exhibited high sensitivity to K(+) and Mn(2+), respectively. It is suggested that the derivatives have potential technological applications in chemosensor fields.

Synthesis and characterization of triphenylethylene derivatives with aggregation-induced emission characteristics.

New aggregation-induced emission (AIE) compounds derived from triphenylethylene were synthesized. The thermal, photophysical, electrochemical and aggregation-induced emissive properties were investigated. All the compounds had strong blue light emission capability and good thermal stability. Their maximum fluorescence emission wavelengths were between 443 to 461 nm in solid states, while their glass transition temperatures ranged from 86 to 129 °C. The decomposition temperatures of the synthesized compounds were in the range of 432-534 °C. The synthesized compounds possessed aggregation-induced emission properties, namely exhibited enhanced fluorescence emission in aggregated states. The highest occupied molecular orbital (HOMO) energy levels estimated from the oxidation potentials were between 5.61 and 5.66 eV and the lowest unoccupied molecular orbital/highest occupied molecular orbital (LUMO/HOMO) energy gap values were found to be in the range of 3.18-3.22 eV. The compounds 4-(4-(2,2-bis(4-(naphthalen-1-yl)phenyl)vinyl)phenyl) dibenzothiophene [(BN)(2)Bt] and 4-(4-(2,2-di(biphenyl-4-yl)vinyl)phenyl) dibenzothiophene [(BB)(2)Bt] exhibited vibronic fine-structure photoluminescence spectra when the water fraction was less than 70%.

Synthesis and properties of diphenylcarbazole triphenylethylene derivatives with aggregation-induced emission, blue light emission and high thermal stability.

New aggregation-induced emission materials derived from diphenylcarbazole triphenylethylene were prepared. The thermal, photophysical, electrochemical and aggregation-induced emissive properties were investigated. All the compounds had strong blue light emission capability and excellent thermal stability. Their maximum fluorescence emission wavelengths were between 450 to 460 nm in TLC plates, while their glass transition temperatures ranged from 162.2 to 182.4 °C. The decomposition temperatures of the synthesized compounds were all well over 500 °C. The synthesized compounds possessed aggregation-induced emission (AIE) properties, which exhibited enhanced fluorescence emissions in aggregation states or in solid states. The HOMO energy levels estimated from the oxidation potentials were found in the range from 5.49 to5.52 eV. The lowest unoccupied molecular orbital/highest occupied molecular orbital (LUMO/HOMO) energy gaps (ΔEg) for the compounds were estimated from the onset absorption wavelengths of UV absorption spectra and ranged from 3.04 to 3.20 eV.

Controlling the thermally activated delayed fluorescence of axially chiral organic emitters and their racemate for information encryption.

A pair of axially chiral organic enantiomers were facilely prepared through a one-pot sequential synthesis. They exhibit circularly polarized luminescence activities and have thermally activated delayed fluorescence (TADF) and aggregation-induced emission enhancement properties. Meanwhile, these two enantiomers present remarkable and reversible thermochromism in the crystalline state, enabling dual-colour TADF switching between orange and red. However, when they form cocrystals, the resulting racemate shows opposite thermochromic behaviors. These intriguing results probably emanate from their different optical activities, leading to distinct molecular packing modes and molecular conformation variations. Moreover, information encryption based on thermochromism of organic enantiomers and their racemate has been presented for the first time. This work may expand the application scope of chiral organic luminogens and pave a new way to construct intelligent luminescent systems.

Reversible and Continuous Color-Tunable Persistent Luminescence of Metal-Free Organic Materials by "Self"-Interface Energy Transfer.

Persistent luminescence from metal-free organic materials is attractive for their ultralong exciton lifetimes. Color-tunable persistent luminescence from single-component organic materials is fascinating but still challenging. By utilizing an efficient approach of "self"-interface energy transfer (IET), the persistent luminescence color of an organic phosphor (CTXO) can be reversibly and continuously tuned by external physical stimuli. Its color circularly changes between green (lifetime = 0.24 s) and deep-yellow (lifetime = 0.10 s) when CTXO is repeatedly triggered with thermal annealing and mechanical grinding. Self-IET from the crystalline part (donor), which exhibits persistent room-temperature phosphorescence, to the amorphous part (acceptor) inside its semicrystal during these treatments is found to be the key exciton process for such novel color modulation. This also provides opportunity for designing stimuli-responsive smart materials with controlled persistent luminescence.

A TPE-benzothiazole piezochromic and acidichromic molecular switch with high solid state luminescent efficiency.

A new organic compound, namely B-TPEAN, was constructed by using tetraphenylethylene, acrylonitrile and benzothiazole as building blocks. Herein, results of single crystal structure analysis and theoretical calculation for the as-synthesized compound were presented. Photophysical properties, including UV-visible absorption, photoluminescence and fluorescent quantum yield, were also well studied. B-TPEAN was found to show excellent aggregation-induced emission (AIE) properties and high quantum yield (up to 85%) in the solid-state. These results should be attributed to the positive effect of a combination of two typical AIE moieties in one molecule. Upon grinding, the emission color of the pristine sample for B-TPEAN changed from bluish green (λ em,max = 497 nm) to yellow (λ em,max = 567 nm), exhibiting a remarkable piezochromism. Moreover, by fuming with acid vapor, both of the pristine and the ground samples of B-TPEAN showed dramatic decreases in fluorescence quantum yields and large bathochromic shifts in PL maxima up to 53 nm and 80 nm, respectively, indicating a success in achieving multi-stimuli-responsive luminophore with high contrast in both emission intensity and color. Further investigation revealed that the acidifluorochormism of the samples was caused by the protonation of the benzothiazole moiety, leading to an enhancement of ICT effect in the protonated molecules.