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 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.

The development of smart-responsive materials, in particular those with non-invasive, rapid responsive phosphorescence, is highly desirable but has rarely been described. Herein, we designed and prepared a series of molecular rotors containing a triazine core and three bromobiphenyl units: o-Br-TRZ, m-Br-TRZ, and p-Br-TRZ. The bromine and triazine moieties serve as room temperature phosphorescence-active units, and the bromobiphenyl units serve as rotors to drive intramolecular rotation. When irradiated with strong ultraviolet photoirradiation, intramolecular rotations of o-Br-TRZ, m-Br-TRZ, and p-Br-TRZ increase, successively resulting in a photothermal effect via molecular motions. Impressively, the photothermal temperature attained by p-Br-TRZ is as high as 102 °C, and synchronously triggers its phosphorescence due to the ordered molecular arrangement after molecular motion. The thermal effect is expected to be important for triggering efficient phosphorescence, and the photon input for providing a precise and non-invasive stimulus. Such sequential photo-thermo-phosphorescence conversion is anticipated to unlock a new stimulus-responsive phosphorescence material without chemicals invasion.

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.

The development of new strategies to construct on-demand porous lattice frameworks from simple motifs is desirable. However, mitigating complexity while combing multiplicity and reversibility in the porous architectures is a challenging task. Herein, based on the synergy of dynamic intermolecular interactions and flexible molecular conformation of a simple cyano-modified tetraphenylethylene tecton, eleven kinetic-stable hydrogen-bonded organic frameworks (HOFs) with various shapes and two thermo-stable non-porous structures with rare perpendicular conformation are obtained. Multimode reversible structural transformations along with visible fluorescence output between porous and non-porous or between different porous forms is realized under different external stimuli. Furthermore, the collaborative of flexible framework and soft long-chain guests facilitate the relaxation from intrinsic blue emission to yellow emission in the excited state, which represents a strategy for generating white-light emission. The dynamic intermolecular interactions, facilitated by flexible molecular conformation and soft guests, diversifies the strategies of construction of versatile smart molecular frameworks.

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.

Persistent luminescence is a fascinating phenomenon with exceptional applications. However, the development of organic materials capable of persistent luminescence, such as organic persistent room-temperature phosphorescence, lags behind for their normally low efficiency. Moreover, enhancing the phosphorescence efficiency of organic luminophores often results in short lifetime, which sets an irreconcilable obstacle. Here we report a strategy to boost the efficiency of phosphorescence by intramolecular triplet-triplet energy transfer. Incorpotation of (bromo)dibenzofuran or (bromo)dibenzothiophene to carbazole has boosted the intersystem crossing and provided an intramolecular triplet-state bridge to offer a near quantitative exothermic triplet–triplet energy transfer to repopulate the lowest triplet-state of carbazole. All these factors work together to contribute the efficient phosphorescence. The generation and transfer of triplet excitons within a single molecule is revealed by low-temperature spectra, energy level and lifetime investigations. The strategy developed here will enable the development of efficient phosphorescent materials for potential high-tech applications., The potential of organic materials with persistent room-temperature phosphorescence for high-tech application is limited by their low efficiency. Here, the authors report a strategy to enhance persistent room-temperature phosphorescence efficiency via intramolecular triplet-triplet energy transfer.

Highly efficient luminescent materials in solid states are promising candidates for the development of organic optoelectrical materials and devices and chemical and biological sensors. Aggregation-induced emission (AIE), a novel photophyscial phenomena coined in 2001 where the aggregate formation enhances the light emission, has drawn great attention because it provides a fantastic platform for the development of these useful luminescent materials. After 17 years of AIE research, diverse AIE luminogens with tunable color and high quantum yields have been explored, which finds diverse applications from optics and electronics to energy and bioscience. Most importantly, the concept of AIE has gradually changed people’s thinking way about the aggregation of luminogen and put forth a revolution of luminogen research both conceptually and technically. This perspective revisits our journey of AIE research, discusses our current understanding of the AIE mechanism, debates current challenges, and looks for the potential breakthroughs in this exciting research area.

The development of single molecule white light emitters is extremely challenging for pure phosphorescent metal-free system at room temperature. Here we report a single pure organic phosphor, namely 4-chlorobenzoyldibenzothiophene, emitting white room temperature phosphorescence with Commission Internationale de l’Éclair-age coordinates of (0.33, 0.35). Experimental and theoretical investigations reveal that the white light emission is emerged from dual phosphorescence, which emit from the first and second excited triplet states. We also demonstrate the validity of the strategy to achieve metal-free pure phosphorescent single molecule white light emitters by intrasystem mixing dual room temperature phosphorescence arising from the low- and high-lying triplet states., The development of single molecule white light-emitters is extremely challenging for pure phosphorescent metal-free systems at room temperature. Here the authors show a single pure organic room temperature phosphor, 4-chlorobenzoyldibenzothiophene, utilizing the emission from both T1 and T2 states.

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 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.

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.

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.

Conjugated macrocycles can be equipped with interesting functions by having polycyclic aromatic hydrocarbon (PAH) building blocks that are larger than benzene. The building block explored herein is phenanthrene, which is connected with varied linkers leading to new trimeric conjugated macrocycles (1–4). The coronal macrocycle 1, whose π-backbone is a new segment of [6,6]-carbon nanotube, is synthesized from the flat macrocycle 2 by Lewis acid-catalyzed [4 + 2] benzannulation. This suggests a new strategy to synthesize π-extended nanorings from conjugated macrocycles that are more easily accessed. As found from a comparative study with focus on self-assembly and organic semiconductor behavior, flat or nearly flat conjugated macrocycles 2–4 function as p-type organic semiconductors in solution-processed thin film transistors. Their field effect mobility as measured from as-cast films is dependent on their ability of self-aggregation in solution.

The poor crystallinity of rubrene in conventional films is a well-known obstacle limiting practical applications of rubrene in thin film transistors. Here we report a study on using 6,13-diazapentacene (DAP) as a template to induce crystallization of rubrene in thin film transistors. This study demonstrates that DAP is a suitable template molecule with negligible contribution to the conduction channel and leads to polycrystalline thin films of rubrene with field effect mobility as high as 0.68 cm2 V−1 s−1. This induced-crystallization strategy highly depends on a unique octadecylphosphonic acid (ODPA) bilayer-step surface, which is found to play important roles in controlling the growth of both DAP and rubrene.