Search

Herein, we realized the quick generation of stable photoinduced radicals in donor–acceptor triarylphosphines with associated color changes of emission and absorption, which was deciphered by the electron paramagnetic resonance (EPR) spectra.

Stable organic radicals are promising materials for information storage, molecular magnetism, electronic devices, and biological probes. Many organic radicals have been prepared, but most are non- ...

The newly emerging circularly-polarized room-temperature phosphorescence (CP-RTP) has experienced rapid growth due to its intriguing photophysical properties and wide-ranging potential applications. Of particular interest are the purely organic CP-RTPs, as they offer excellent biocompatibility, versatile tunability, and cost-effectiveness. Therefore, these materials show promising applications, including biological imaging, photodiodes, intelligent sensing, information storage, and three-dimensional displays. To deepen our understanding of the luminescence mechanism and broaden the envisioned scope, herein, we summarize them based on chirality character, including point, axial, planar, and other chiral systems. This review aims to scrutinize missing clues and envision future development of the area.

Boosting the circularly polarized luminescence of small organic molecules has been a stubborn challenge because of weak structure rigidity and dynamic molecular motions. To investigate and eliminate these factors, here, we carried out the struc-ture-property relationship studies on a newly-developed axial chiral scaffold of bidibenzo[b,d]furan. The molecular rigidity was finely tuned by gradually reducing the alkyl-chain length. The environmental factors were considered in solution, crystal, and polymer matrix at different temperatures. As a result, a significant amplification of the dissymmetry factor glum from 10-4 to 10-1 with a 146-fold magnification was achieved, corresponding to the situation from (R)-4C in solution to (R)-1C in polymer film at room temperature. A synergistic strategy of increasing the intramolecular rigidity and enhancing the inter-molecular interaction to restrict the molecular motions was thus proposed to improve circularly polarized luminescence. The though-out demonstrated relationship will be of great importance for the development of high-performance small organic chiroptical systems in the future.

Cells are responsive to the mechanical environment, but the methods to detect simultaneously how different organelles react in mechanobiological processes remain largely unexplored. We herein report a dual organelle-targeting fluorescent probe, ( E )-1-[3-(diethoxyphosphoryl)propyl]-4-[4-(diethylamino)styryl]pyridin-1-ium bromide (ASP-PE), for mechanical mapping in live cells. ASP-PE is aggregation-induced emission active and is sensitive to the local mechanical environment. It targets the plasma membrane (PM) and intracellular mitochondria in cells by its phosphonate moiety and pyridinium. In this work, through ASP-PE staining, changes of membrane tension in the PM and mitochondria in response to varied osmotic pressure and substrate stiffness are visualized using fluorescence lifetime imaging microscopy. The mechanobiological importance of actin filaments and microtubules in the PM and mitochondria is also investigated using this probe. Computational simulations are applied to study the sensing mechanism of the probe. This study introduces a unique tool for mapping the membrane tension in the PM and mitochondria together, providing us great opportunities to study organelle’s interactions in mechanobiology.

The construction of molecular chirality is crucial for exploring novel luminophores with chiroptical properties. Classic asymmetric synthesis of chiral center or axial is not powerful enough on through-space architecture. Accessible methodologies for breaking molecular symmetry could be promising but remain less investigated. Herein, we report a novel methodology for constructing chiral through-space luminophores via simple chlorination on bridged carbazole motifs. The chlorination breaks the molecular symmetry and thus results in molecular chirality by eliminating the mirror plane or rotating axis. Interestingly, continuous multiple chlorinations can rebuild and break the symmetry of the skeleton in succession. Several chiral and achiral isomeric analogues are synthesized and characterized with impressive chiroptical properties. Results of chiral HPLC, single-crystal X-ray diffraction, kinetic racemization, and chiroptical property investigation demonstrate the effectiveness of our rational design strategy. It provides a feasible methodology for exploring novel chiral luminescent materials based on versatile though-space skeletons.

Room temperature phosphorescence (RTP) and mechanoluminescence (ML) materials are in high demand because of their promising applications in optoelectronic devices. However, most materials bear only one of these properties and molecules bearing both of them are rarely reported. Here, we report a carbazole derivative 1, which displays both RTP activity and near-ultraviolet ML properties. These properties are highly related to the packing modes and molecular configuration as revealed by the analysis of their crystal structures and theoretical calculations. The near-ultraviolet ML of 1 can further serve as the exciting light source to transfer its energy to luminescent dyes to realize colorful ML. The thermal-responsive RTP of 1 can be utilized to prepare anti-counterfeiting tags for simple security protection. This work has put forward a simple but efficient strategy to prepare multifunctional molecular systems bearing both RTP and ML properties.

Triplet excitons in organic molecules underscore a variety of processes and technologies as a result of their long lifetime and spin multiplicity. Organic phosphorescence, which originates from triplet excitons, has potential for the development of a new generation of organic optoelectronic materials and biomedical agents. However, organic phosphorescence is typically only observed at cryogenic temperatures and under inert conditions in solution, which severely restricts its practical applications. In the past few years, room-temperature-phosphorescent systems have been obtained based on organic aggregates. Rapid advances in molecular-structure design and aggregation-behaviour modulation have enabled substantial progress, but the mechanistic picture is still not fully understood because of the high sensitivity and complexity of triplet-exciton behaviour. This Review analyses key photophysical processes related to triplet excitons, including intersystem crossing, radiative and non-radiative decay, and quenching processes, to illustrate the intrinsic structure–property relationships and draw clear and integrated design principles. The resulting strategies for the development of efficient and persistent room-temperature-phosphorescent systems are discussed, and newly emerged applications based on these materials are highlighted. Advances in molecular-structure design and modulation of the aggregation behaviour have enabled much progress in the observation of room-temperature phosphorescence from organic aggregates. This Review analyses key photophysical processes related to triplet excitons, illustrating the intrinsic structure–property relationships and identifying strategies to design efficient and persistent room-temperature-phosphorescent systems.

Polymorphism of organic semiconductor films is of key importance for the performance of organic thin film transistors (OTFTs). Herein, we demonstrate that the polymorphism of solution-processed organic semiconductors in thin film transistors can be controlled by finely tuning the surface nanostructures of substrates with self-assembled monolayers (SAMs). It is found that the SAMs of 12-cyclohexyldodecylphosphonic acid (CDPA) and 12-phenyldodecylphosphonic acid (PhDPA) induce different polymorphs in the dip-coated films of 2-dodecyl[1]benzothieno[3,2-b][1]benzothiophene (BTBT-C12). The film of BTBT-C12 on CDPA exhibits field effect mobility as high as 28.1 cm2 V−1 s−1 for holes, which is higher than that of BTBT-C12 on PhDPA by three times. The high mobility of BTBT C12 on CDPA is attributable to the highly oriented films of BTBT C12 with a reduced in-plane lattice and high molecular alignment.

Novel accessible scaffold featuring circularly-polarized room-temperature phosphorescence (RTP) is attractive but challenging. Herein, we report a new feasibly separable bidibenzo[b,d]furan compound with strong circularly-polarized RTP when doping into the rigid polymer matrix. The simple silica-gel column can separate the absolute chiral R-isomer with excellent chiroptical properties. The experimental data reveal that the treated films exhibit an RTP efficiency of 14.8 %, a largest dissymmetric factor of 0.12, and a longest lifetime of 0.56 s under ambient conditions. It is found that reducing the nonradiative decays boosts the intrinsic circularly-polarized RTP emission. The impressive results indicate that the locked axial chirality skeleton endows the potential of achieving superior circularly-polarized emission for the small organic optoelectronic molecules.

Research on molecularly imprinted polymers (MIPs) has long been receiving much attention, but issues concerning the recognition mechanism and how the impact factors work are still far from clear. In this work, we studied the imprinting and recognition procedures from a new perspective. Two factors that have a major impact on the imprinting performance were studied separately: one is the functional groups (FGs) of the template and the other is the size of the template. A series of aggregation-induced emission molecules (AIEgens) was employed as the templates, and they were selected elaborately, one group of which having different functional groups with a similar size, while the other being different in molecular size. It was found that the MIP was inclined to combine with molecules with more effective functional groups or with smaller sizes. Meanwhile, the more ordered sites and the larger cavities in the polymers afforded the MIP with better adsorption performance. The binding energy (ΔE) and the mechanism at the molecular level between templates and polymers were analyzed by using density functional theory (DFT) calculations, and the results were consistent with experimental results in the aspect of the FG effect. In addition, the unique luminescence properties of AIEgens allow for visible observation of the change of the template within the polymer during preparation and rebinding processes. More importantly, quantification of template molecules during the adsorption process was fulfilled based on their solid-state fluorescence intensities, which opens a new door for AIEgen application. A comparison with the common method of UV-vis spectrometry revealed that solid-state fluorescence measurement has the advantages of direct detection, easy operation, a wide linear range and so on.

A pentagonal macrocycle (MC5-PER) with radialene topology was facilely synthesized through a selective one-pot Suzuki-Miyaura cross-coupling reaction. The resulting product is endowed with a pentagonal architecture as revealed by its single crystal structure, which affords the smallest ring strain and the best conjugation. As tetraphenylethene subunits are embedded, MC5-PER is highly emissive in the solid state due to the aggregation-induced emission effect. Because of the flexible structure and preferable fibre-like self-assembly, the aggregate of MC5-PER displays interesting polymorphism-dependent emission and acts as a sensitive fluorescence sensor for explosives detection.

Many aggregation-induced emission (AIE) materials are featured by the diphenylethene (DPE) moiety which exhibits rich photophysical and photochemical activities. The understanding of these activities behind AIE is essential to guide the design of fluorescent materials with improved performance. Herein by fusing a flexible DPE with a rigid spiro scaffold, we report a class of novel deep-blue material with solid-state fluorescent quantum yield (ΦF) up to 99.8%. Along with the AIE phenomenon, we identified a reversible photocyclization (PC) on DPE with visible chromism, which is, on the contrary, popularized in solutions but blocked by aggregation. We studied the steric and electronic effects of structural perturbation and concluded that the PC is a key process behind the RIMs (restriction of intramolecular motions) mechanism for these materials. Mitigation of the PC leads to enhanced fluorescence in solutions and loss of the AIE characteristics.

Herein, we report a simple approach to generate stableluminescent radicals in the presence of gentle UV irradiation. The newly generated radicalspecies are capable of emitting unusual red light with a maximum fluorescence quantumefficiency of 4.6% at ambient conditions in the solid state. Additionally, the luminescentradicals show extraordinary stability with more than one-year life-span at ambient conditions.X-ray diffraction study combined with photophysical and computational analyses reveal thatthe unique molecular symmetry breaking in the crystalline state lead to the unusual formationand stabilization of radical ion pairs via the photo-induced electron transfer (PET) process. Suchresults represent the first time to achieve stable emissive radicals in the solid state at ambientconditions via in-situ PET process.

Controlling molecular assembled structures of a single luminogen through external manipulation is a general and powerful concept for designing emission-tunable materials. However, these reported powder-like compounds generally show limited emission color, high serendipitous-discovery dependence and poor mechanical properties. To overcome these limitations, we describe a simple yet powerful strategy that is adapted from methods used to control bulk commodity polymers, to modulate the molecular assembled architecture of dopant. We use luminogens with aggregation-induced emission characteristics and intrinsic blue and yellow emissions at their crystalline and amorphous states as demonstrations. When incorporating such luminogens (AIEgens) in the desired polymer matrix with tailored microstructure, white light and white circularly polarized light are generated, which are inaccessible from single and achiral AIEgen alone. The introduced strategy for realizing diverse light emission is an innovative way of developing luminogens and provides useful continuous emissive materials in the forms of macroscopic films and fibers for developing flexible devices and wearable systems.

Background The current debate over the optimal Enoxaparin prophylactic dosing strategies in obese patients centre around whether it should be based on the actual weight of the patient (i.e. weight-based), or at an artificially fixed amount, as it is the case in Australia (40 mg daily). The vast majority of the evidence available today is laboratory-based, measuring serum Antifactor-X a activities as a marker for physiological response. Aim The aim of the parent study is to compare the clinical outcomes for obese patients who received fixed doses of enoxaparin compared to those who received weight-based doses within the licensed dosage recommendations. This review was conducted to examine whether a gap in knowledge exists in relation to dosing obese patients with enoxaparin as VTE prophylaxis after hospital admission to aid in development of the parent study concept. Method Databases such as Medline, EBSCOhost, ProQuest were interrogated using combinations of words such as “enoxaparin”, AND “dosing strategy”, AND “obese/obesity” AND “prophylaxis”. Only eleven out of 14 primary studies which were considered to be sufficiently similar in methodology and anticipated outcomes were reviewed and analysed. Results Pooled data from the eleven studies suggested that weight-based or higher-than-fixed dosing had a 36.2% higher success rate than fixed dosing, and was more likely to achieve the desired serum Anti-X a activity levels (52.2% and 16% respectively). The rate of failure to achieve this is significantly lower in the weight-based groups (13.3%) than in fixed-dose groups (18.5%). These eleven studies reviewed included 601 patients in total. Conclusion There is insufficient evidence to support or negate the current enoxaparin health outcomes in obese and very obese patients due to the lack of post-discharge follow-up from hospitals. Further research is required to compare long-term outcomes after fixed and weight-based dosing of enoxaparin. The optimal dose of enoxaparin per kilogram of body weight for prophylaxis remains to be determined.

Because of their innate ability to store and then release energy, long-persistent luminescence (LPL) materials have garnered strong research interest in a wide range of multidisciplinary fields, such as biomedical sciences, theranostics, and photonic devices. Although many inorganic LPL systems with afterglow durations of up to hours and days have been reported, organic systems have had difficulties reaching similar timescales. In this work, a design principle based on the successes of inorganic systems to produce an organic LPL (OLPL) system through the use of a strong organic electron trap is proposed. The resulting system generates detectable afterglow for up to 7 h, significantly longer than any other reported OLPL system. The design strategy demonstrates an easy methodology to develop organic long-persistent phosphors, opening the door to new OLPL materials.

Because of their innate ability to store and then release energy, long persistent luminescence (LPL) materials have garnered strong research interest in a wide range of multidisciplinary fields, such as biomedical sciences, theranostics, and photonic devices. Although many inorganic LPL systems with afterglow durations of up to hours and days have been reported, organic LPL (OLPL) systems have had difficulties reaching similar timescales. We propose in this work a design principle based on the successes of inorganic systems to produce an OLPL system through the use of a strong organic electron trap. The resulting system generated detectable afterglow for up to 7 hours, significantly longer than any other reported OLPL system. The design strategy demonstrates an easy methodology to develop organic long persistent phosphors, opening the door to new OLPL materials.

An antibody–AIEgen conjugate is designed and developed as a “turn-on” fluorescent probe for wash-free specific cancer cell imaging. The cetuximab-conjugated AIEgen shows red fluorescence only when it is internalized and accumulated in cancer cells with overexpressed epidermal growth factor receptor through endocytosis. The probe first lights up the lysosomes. After hydrolysis, its residue is accumulated in mitochondria, making them highly emissive with a long cell retention time. Compared with conventional “always-on” fluorescent probes, the antibody–AIEgen conjugate exhibits a very good image contrast during wash-free cancer cell imaging and less interference from normal cells. To the best of our knowledge, this is the first time “turn-on” antibody–AIEgen conjugates have been reported. This new strategy can be further extended to many proteins and water-soluble AIEgens, and many of their potential applications such as real-time tracking of cell dynamics and cancer theranostics will be explored. The present work is expected to inspire more marvellous research in the fields of AIE and cancer imaging.

Summary Manipulation of the emission properties of pure organic room-temperature phosphors through molecular design is attractive but challenging. Tremendous efforts have been made to modulate their aggregation behaviors to suppress nonradiative decay in order to achieve efficient light emission and long lifetimes. However, success has been limited. To attain such a goal, here we present a rational design principle based on intrinsic molecular-structure engineering. Comprehensive investigations on the molecular orbitals revealed that an excited state with hybrid (n,π*) and (π,π*) configurations in appreciable proportion is desired. Tailoring the aromatic subunits in arylphenones can effectively tune the energy level and the orbital feature of the triplet exciton. Our experimental data reveal that a series of full-color pure organic phosphors with a balanced lifetime (up to 0.23 s) and efficiency (up to 36.0%) can be realized under ambient conditions, demonstrating the validity of our instructive design principle.

The development of solid-state intelligent materials, in particular those showing photoresponsive luminescence (PRL), is highly desirable for their cutting-edge applications in sensors, displays, data-storage, and anti-counterfeiting, but is challenging. Few PRL materials are constructed by tethering the classic photochromic systems with newly-emerged solid-state emitters. Selective solid-state photoreactions are demanded to precisely manipulate the luminescent behavior of these emitters, which require dramatic structural change and enough free space, thus limiting the scope of the PRL family. Here, a new PRL material, TPE-4N, that features sensitive and reversible fluorescence switching is reported. The interesting on-off luminescent property of TPE-4N can be facilely tuned through fast phototriggering and thermal annealing. Experimental and theoretical investigations reveal that subtle molecular conformation variation induces the corresponding PRL behavior. The crystalline and amorphous state endows an efficient and weak ISC process, respectively, to turn on and off the emission. The readily fabricated thin-film of TPE-4N exhibits non-destructive PRL behavior with high contrast (>102 ), good light transmittance (>72.3%), and great durability and reversibility under room light for months. Remarkably, a uniform thin-film with such fascinating PRL properties allows high-tech applications in invisible anti-counterfeiting and dynamic optical data storage with micro-resolution.

Poly(1,5-diaminonaphthalene) microparticles with abundant reactive amino and imino groups on their surface were synthesized by one-step oxidative polymerization of 1,5-diaminonaphthalene using ammonium persulfate as the oxidant. The molecular, supramolecular, and morphological structures of the microparticles were systematically characterized by IR and UV-vis spectroscopies, elementary analysis, wide-angle X-ray diffractometry, and transmission electron microscopy. The microparticles demonstrate electrical semiconductivity and high resistance to strong acid and alkali, and strong adsorption capability for lead(II), mercury(II), and silver(I) ions. The experimental conditions for adsorption of Pb(II) were optimized by varying the persulfate/monomer ratio, adsorption time, sorbent concentration, and pH value of the Pb(II) solution. The maximum adsorption capacity is 241 mg·g−1 for particles after a 24 h-exposure to a solution at an initial Pb(II) concentration of 29 mM. The adsorption data fit a Langmuir isotherm and follow a pseudo-second-order reaction kinetics. This indicates a chemical adsorption that is typical for a chelation interaction between Pb(II) and amino/imino groups on the sorbent.

The development of intelligent materials, in particular those showing the highly sensitive mechanoresponsive luminescence (MRL), is desirable but challenging. Here we report a design strategy for constructing high performance On–Off MRL materials by introducing nitrophenyl groups to molecules with aggregation-induced emission (AIE) characteristic. The on–off methodology employed is based on the control of the intersystem crossing (ISC) process. Experimental and theoretical investigations reveal that the nitrophenyl group effectively opens the nonradiative ISC channel to impart the high sensitivity and contrast On–Off behavior. On the other hand, the twisted AIE luminogen core endows enhanced reversibility and reduces the pressure required for the luminescence switching. Thin films can be readily fabricated from the designed materials to allow versatile applications in optical information recording and haptic sensing. The proposed design strategy thus provides a big step to expand the scope of the unique On–Off MRL family., The development of intelligent materials, in particular those showing the highly sensitive mechanoresponsive luminescence (MRL), remains challenging. Here the authors report a strategy for constructing high performance On-Off MRL materials by introducing nitrophenyl groups to molecules with aggregation-induced emission characteristic.

We present a nitrogen-containing polycyclic aromatic hydrocarbon (N-PAH), namely 12-methoxy-9-(4-methoxyphenyl)-5,8-diphenyl-4-(pyridin-4-yl) pyreno[1,10,9-h,i,j]-isoquinoline (c-TPE-ON), which exhibits high quantum-yield emission both in solution (blue) and in the solid state (yellow). This molecule was unexpectedly obtained by a three-fold, highly regioselective photocyclodehydrogenation of a tetraphenylethylene-derived AIEgen. Based on manifold approaches involving UV/Vis, photoluminescence, and NMR spectroscopy as well as HRMS, we propose a reasonable mechanism for the formation of the disk-like N-PAH that is supported by density functional theory calculations. In contrast to most PAHs that are commonly used, our system does not suffer from entire fluorescence quenching in the solid state due to the peripheral aromatic rings preventing p-p stacking interactions, as evidenced by single-crystal X-ray analysis. Moreover, its rod-like microcrystals exhibit excellent optical waveguide properties. Hence, c-TPE-ON comprises a N-PAH with unprecedented luminescent properties and as such is a promising candidate for fabricating organic optoelectronic devices. Our design and synthetic strategy might lead to a more general approach to the preparation of solution-and solid-state luminescent PAHs.

Organic fluorophores with reversible emission switching behavior are promising materials for applications in sensors, optical recording, security inks, and optoelectronics. A variety of aggregation-induced emission (AIE) luminogens with mechanochromic luminescence has been prepared, and the transformation of efficient bluer-emitting crystals to amorphous powders with redder and weaker emission is proposed to be the cause for such behavior. However, detailed mechanistic understanding from experimental to theoretical is lacking. In this work, we present the design and synthesis of a group of bis(diarylmethylene)dihydroanthracenes with butterfly-like shapes. These molecules exhibit aggregation-induced emission characteristics due to the restriction of intramolecular motion in the aggregated state. They show mechanochromism, because of the transformation between crystal and amorphous states with different colors and efficiencies aided by grinding/heating or solvent fuming processes. By investigation of their ...

The facile synthesis of a tetraphenylethene-based macrocycle having aggregation-induced emission characteristics and that expresses illusory topology of the Penrose stairs is presented. As a result of the twisted chirality (P or M) of the tetraphenylethene unit and the axial chirality of the macrocyclic linkage (R or S), the macrocycle exhibits two absolute configurations whose interconversion is energetically favorable as revealed by theoretical calculations.

Herein we reported a new facile one-pot multicomponent sequential polymerization approach for the construction of conjugated nitrogen-substituted polymers. Catalyzed by Pd(PPh3)2Cl2/CuI at room temperature, the coupling-hydroamination polymerizations of 1,2-bis(4-ethynylphenyl)-1,2-diphenylethene, terephthaloyl chloride and secondary aliphatic amines proceeded smoothly in a regioregular and stereoselective manner, furnishing poly(arylene enaminone)s (PAEs) with high molecular weights (Mw up to 34 600) in satisfactory yields (up to 91%). A model compound was elaborately designed and synthesized to verify the chemical structures of the corresponding polymeric products. All the PAEs exhibited good solubility in common organic solvents and were thermally stable with degradation temperatures of up to 313 °C under nitrogen. They possessed good film-forming ability and their thin solid films showed high refractive indices (RI = 1.9318–1.6320) in a wide wavelength region of 400–1000 nm, whose value could be further modulated by UV irradiation. Although the model compound and the PAEs possessed a typical aggregation-induced emission luminogen of tetraphenylethene, they were weakly emissive either in solution or in the aggregated state, due to the photoinduced electron transfer (PET) effect. Their strong emission in the aggregated state could be readily recovered by the blockage of the PET effect through protonation of the amino groups. Thus, this work demonstrated a powerful polymerization tool to access conjugated polymeric materials with pH-responsive properties.

Solid-state photochromism was found in bis(diphenylmethylene)dihydrotetracene, caused by photocyclization of the embedded cis-stilbene motifs., Reported herein is a new class of pure polycyclic hydrocarbon molecules, designed through a novel aggregation-induced emission (AIE) strategy, with unexpected photochromic properties. The restriction of intramolecular motion was found as a comprehensive mechanism for the AIE effect. The photochromism mechanism study revealed that the photocyclization reaction of cis-stilbene, the molecular conformation in the single crystal and the tetracene backbone should contribute to the unique photo behavior. In particular, the fast responsive, photo-reversible and thermo-irreversible photochromic effect facilitated in the solid state opens a new field of aggregation-promoted photochromism.

π-Bonds connected with aromatic rings were generally believed as the standard structures for constructing highly efficient fluorophores. Materials without these typical structures, however, exhibited only low fluorescence quantum yields and emitted in the ultraviolet spectral region. In this work, three molecules, namely bis(2,4,5-trimethylphenyl)methane, 1,1,2,2-tetrakis(2,4,5-trimethylphenyl)ethane, and 1,1,2,2-tetraphenylethane, with nonconjugated structures and isolated phenyl rings were synthesized and their photophysical properties were systematically investigated. Interestingly, the emission spectra of these three molecules could be well extended to 600 nm with high solid-state quantum yields of up to 70%. Experimental and theoretical analyses proved that intramolecular through-space conjugation between the “isolated” phenyl rings played an important role for this abnormal phenomenon.

Photosensitizers are generally treated as key components for photodynamic therapy. In contrast, we herein report an aggregation-induced emission luminogen (AIEgen)-based photosensitizer (TPE-Py-FFGYSA) that can serve as a non-toxic adjuvant to amplify the antitumor efficacy of paclitaxel, a well-known anticancer drug, with a synergistic effect of "0 + 1 > 1". Besides the adjuvant function, TPE-Py-FFGYSA can selectively light up EphA2 protein clusters overexpressed in cancer cells in a fluorescence turn-on mode, by taking advantage of the specific YSA peptide (YSAYPDSVPMMS)-EphA2 protein interaction. The simple incorporation of FFG as a self-assembly-aided unit between AIEgen (TPE-Py) and YSA significantly enhances the fluorescent signal output of TPE-Py when imaging EphA2 clusters in live cancer cells. Cytotoxicity and western blot studies reveal that the reactive oxygen species (ROS) generated by TPE-Py-FFGYSA upon exposure to light do not kill cancer cells, but instead provide an intracellular oxidative environment to help paclitaxel have much better efficacy. This study thus not only extends the application scope of photosensitizers, but also offers a unique theranostic system with the combination of diagnostic imaging and adjuvant antitumor therapy.

A novel dark through-bond energy transfer (DTBET) strategy is proposed and applied as the design strategy to develop ratiometric Hg2+ sensors with high performance. Tetraphenylethene (TPE) derivatives with aggregation-induced emission (AIE) characteristics are selected as dark donors to eliminate emission leakage from the donors. The TBET mechanism has been adopted since it experiences less influence from spectral overlapping than Forster resonance energy transfer (FRET), making it more flexible for developing cassettes with large pseudo-Stokes shifts. In this work, energy transfer from the TPE derivatives (dark donor) to a rhodamine moiety (acceptor) was illustrated through photophysical spectroscopic studies and the energy transfer efficiency (ETE) was found to be up to 99%. In the solution state, no emission from the donors was observed and large pseudo-Stokes shifts were achieved (>280 nm), which are beneficial for biological imaging. Theoretical calculations were performed to gain a deeper mechanistic insight into the DTBET process and the structure-property relationship of the DTBET cassettes. Ratiometric Hg2+ sensors were rationally constructed based on the DTBET mechanism by taking advantage of the intense emission of TPE aggregates. The Hg2+ sensors exhibited well resolved emission peaks. >6000-fold ratiometric fluorescent enhancement is also achieved and the detection limit was found to be as low as 0.3 ppb. This newly proposed DTBET mechanism could be used to develop novel ratiometric sensors for various analytes and AIEgens with DTBET characteristics will have great potential in various areas including light harvesting materials, environmental science, chemical sensing, biological imaging and diagnostics.

A novel dark through-bond energy transfer (DTBET) strategy is proposed and applied as the design strategy to develop ratiometric Hg2+ sensors with high performance., A novel dark through-bond energy transfer (DTBET) strategy is proposed and applied as the design strategy to develop ratiometric Hg2+ sensors with high performance. Tetraphenylethene (TPE) derivatives with aggregation-induced emission (AIE) characteristics are selected as dark donors to eliminate emission leakage from the donors. The TBET mechanism has been adopted since it experiences less influence from spectral overlapping than Förster resonance energy transfer (FRET), making it more flexible for developing cassettes with large pseudo-Stokes shifts. In this work, energy transfer from the TPE derivatives (dark donor) to a rhodamine moiety (acceptor) was illustrated through photophysical spectroscopic studies and the energy transfer efficiency (ETE) was found to be up to 99%. In the solution state, no emission from the donors was observed and large pseudo-Stokes shifts were achieved (>280 nm), which are beneficial for biological imaging. Theoretical calculations were performed to gain a deeper mechanistic insight into the DTBET process and the structure–property relationship of the DTBET cassettes. Ratiometric Hg2+ sensors were rationally constructed based on the DTBET mechanism by taking advantage of the intense emission of TPE aggregates. The Hg2+ sensors exhibited well resolved emission peaks. >6000-fold ratiometric fluorescent enhancement is also achieved and the detection limit was found to be as low as 0.3 ppb. This newly proposed DTBET mechanism could be used to develop novel ratiometric sensors for various analytes and AIEgens with DTBET characteristics will have great potential in various areas including light harvesting materials, environmental science, chemical sensing, biological imaging and diagnostics.

Herein, two novel N-phenylated N-heteroacenes (1 and 2) are reported, along with details of their synthesis, structures, and properties. Compound 1 is a N-hetero analogue of rubrene, but differs from rubrene by having a bent backbone and behaving as an insulator in the solid state owing to the lack of π-π interactions. Compound 2 is a N-hetero analogue of 6,13-diphenylpentacene (DPP) with essentially the same molecular geometry and crystal packing as DPP, but exhibiting a field effect mobility higher than that of DPP by two orders of magnitude.

Novel silylethynylated N-heteropentacenes that have three adjacent pyrazine rings at the center of a pentacene backbone are reported. These hexaazapentacenes exhibit a record low energy level of lowest unoccupied molecular orbital (LUMO) for N-heteropentacenes and thus are able to oxidize dihydroanthracene to anthracene. Their synthetic precursors are the corresponding dihydrohexaazapentacenes, which exhibit interesting H-bonding.