Dual-Phase Thermally Activated Delayed Fluorescence Luminogens: A Material for Time-Resolved Imaging Independent of Probe Pretreatment and Probe Concentration

Developing luminescent probes with long lifetime and high emission efficiency is essential for time-resolved imaging. However, the practical applications usually suffer from emission quenching of traditional luminogens in aggregated states, or from weak emission of aggregation-induced emission type luminogens in monomeric states. Herein, we overcome this dilemma by a rigid-and-flexible alternation design in donor–acceptor–donor skeletons, to achieve a thermally activated delayed fluorescence luminogen with high emission efficiency both in the monomeric state (quantum yield up to 35.3 %) and in the aggregated state (quantum yield up to 30.8 %). Such a dual-phase strong and long-lived emission allows a time-resolved luminescence imaging, with an efficiency independent of probe pretreatment and probe concentration. The findings open opportunities for developing luminescent probes with a usage in larger temporal and spatial scales.     

Structural Engineering of Luminogens with High Emission Efficiency Both in Solution and in the Solid State

Developing molecules with high emission efficiency both in solution and the solid state is still a great challenge, since most organic luminogens are either aggregation‐caused quenching or aggregation‐induced emission molecules. This dilemma was overcome by integrating planar and distorted structures with long alkyl side chains to achieve DAπAD type emitters. A linear diphenyl–diacetylene core and the charge transfer effect ensure considerable planarity of these molecules in the excited state, allowing strong emission in dilute solution (quantum yield up to 98.2 %). On the other hand, intermolecular interactions of two distorted cyanostilbene units restrict molecular vibration and rotation, and long alkyl chains reduce the quenching effect of the π–π stacking to the excimer, eventually leading to strong emission in the solid state (quantum yield up to 60.7 %).     

A Single‐Wavelength‐Emitting Ratiometric Probe Based on Phototriggered Fluorescence Switching of Graphene Quantum Dots

Ratiometric fluorescent probes are of great importance in research, because a built‐in correction for environmental effects can be provided to reduce background interference. However, the traditional ratiometric fluorescent probes require two luminescent materials with different emission bands. Herein a novel ratiometric probe based on a single‐wavelength‐emitting material is reported. The probe works by regulating the luminescent property of graphene quantum dots with UV illumination as activator. The ratiometric sensor shows high sensitivity and specificity for iron ions. Moreover, the ratiometric sensor was successfully employed to monitor ferritin levels in Sprague Dawley rats with chemical‐induced acute liver damage. The proposed single‐wavelength ratiometric fluorescent probe may greatly broaden the applicability of ratiometric sensors in diagnostic devices, medical applications, and analytical chemistry.     

Integrating Time‐Resolved Imaging Information by Single‐Luminophore Dual Thermally Activated Delayed Fluorescence

The fact that the lifetime of photoluminescence is often difficult to access because of the weakness of the emission signals, seriously limits the possibility to gain local bioimaging information in time‐resolved luminescence probing. We aim to provide a solution to this problem by creating a general photophysical strategy based on the use of molecular probes designed for single‐luminophore dual thermally activated delayed fluorescence (TADF). The structural and conformational design makes the dual TADF strong in both diluted solution and in an aggregated state, thereby reducing sensitivity to oxygen quenching and enabling a unique dual‐channel time‐resolved imaging capability. As the two TADF signals show mutual complementarity during probing, a dual‐channel means that lifetime mapping is established to reduce the time‐resolved imaging distortion by 30–40 %. Consequently, the leading intracellular local imaging information is serialized and integrated, which allows comparison to any single time‐resolved signal, and leads to a significant improvement of the probing capacity.     

Simultaneous Long‐Persistent Blue Luminescence and High Quantum Yield within 2D Organic–Metal Halide Perovskite Micro/Nanosheets

Molecular solid‐state materials with long‐lived luminescence (such as thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) systems) are promising for display, sensoring, and bio‐imaging applications. However, the design of such materials that exhibit both long luminescent lifetime and high solid‐state emissive efficiency remains an open challenge. Two‐dimensional (2D) organic–metal halide perovskite materials have a high blue‐emitting quantum yield of up to 63.55 % and ultralong TADF lifetime of 103.12 ms at ambient temperature and atmosphere. Our design leverages the combined influences of a 2D space/electronic confinement effect and a modest heavy‐atom tuning strategy. Photophysical studies and calculations reveal that the enhanced quantum yield is due to the rigid laminate structure of perovskites, which can effectively inhibit the non‐radiative decay of excitons.     

Slow geminate‐charge‐pair recombination dynamics at polymer: Fullerene heterojunctions in efficient organic solar cells

We explore charge recombination dynamics at electron donor‐acceptor heterojunctions, formed between a semiconductor polymer (PCDTBT) and a fullerene derivative (PC₇₀BM), by means of combined time‐resolved photoluminescence and transient absorption spectroscopies. Following prompt exciton dissociation across the heterojunction, a subset of bound electron‐hole pairs recombines with a temperature‐independent rate distribution spanning submicrosecond timescales to produce luminescent charge‐transfer excitons (CTX). At 14 K, this slow mechanism is the dominant geminate charge recombination pathway, whereas we also observe CTX emission on subnanosecond timescales at 293 K. We thus find that at these temperatures, a fraction of the initial charge‐pair population is trapped deeply such that they only recombine slowly over a broad distribution of timescales by quantum tunneling. We identify geminate polaron pairs (GPP) as a reservoir of long‐lived localized states that repopulate the CTX up to microsecond timescales. The observation of such distributed geminate‐charge recombination highlights the importance of the molecular nature of specific donor–acceptor electronic interactions in defining the relaxation pathways of trapped GPP. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

An Organic Molecule with Asymmetric Structure Exhibiting Aggregation‐Induced Emission,Delayed Fluorescence,and Mechanoluminescence

Compounds displaying delayed fluorescence (DF), from severe concentration quenching, have limited applications as nondoped organic light‐emitting diodes and material sciences. As a nondoped fluorescent emitter, aggregation‐induced emission (AIE) materials show high emission efficiency in their aggregated states. Reported herein is an AIE‐active, DF compound in which the molecular interaction is modulated, thereby promoting triplet harvesting in the solid state with a high photoluminescence quantum yield of 93.3 %, which is the highest quantum yield, to the best of our knowledge, for long‐lifetime emitters. Simultaneously, the compound with asymmetric molecular structure exhibited strong mechanoluminescence (ML) without pretreatment in the solid state, thus exploiting a design and synthetic strategy to integrate the features of DF, AIE, and ML into one compound.     

An Organic Molecule with Asymmetric Structure Exhibiting Aggregation‐Induced Emission,Delayed Fluorescence,and Mechanoluminescence

Compounds displaying delayed fluorescence (DF), from severe concentration quenching, have limited applications as nondoped organic light‐emitting diodes and material sciences. As a nondoped fluorescent emitter, aggregation‐induced emission (AIE) materials show high emission efficiency in their aggregated states. Reported herein is an AIE‐active, DF compound in which the molecular interaction is modulated, thereby promoting triplet harvesting in the solid state with a high photoluminescence quantum yield of 93.3 %, which is the highest quantum yield, to the best of our knowledge, for long‐lifetime emitters. Simultaneously, the compound with asymmetric molecular structure exhibited strong mechanoluminescence (ML) without pretreatment in the solid state, thus exploiting a design and synthetic strategy to integrate the features of DF, AIE, and ML into one compound.     

High‐Performance Non‐doped OLEDs with Nearly 100 % Exciton Use and Negligible Efficiency Roll‐Off

Non‐doped organic light‐emitting diodes (OLEDs) possess merits of higher stability and easier fabrication than doped devices. However, luminescent materials with high exciton use are generally unsuitable for non‐doped OLEDs because of severe emission quenching and exciton annihilation in neat films. Herein, we wish to report a novel molecular design of integrating aggregation‐induced delayed fluorescence (AIDF) moiety within host materials to explore efficient luminogens for non‐doped OLEDs. By grafting 4‐(phenoxazin‐10‐yl)benzoyl to common host materials, we develop a series of new luminescent materials with prominent AIDF property. Their neat films fluoresce strongly and can fully harvest both singlet and triplet excitons with suppressed exciton annihilation. Non‐doped OLEDs of these AIDF luminogens exhibit excellent luminance (ca. 100000 cd m^?2), outstanding external quantum efficiencies (21.4–22.6 %), negligible efficiency roll‐off and improved operational stability. To the best of our knowledge, these are the most efficient non‐doped OLEDs reported so far. This convenient and versatile molecular design is of high significance for the advance of non‐doped OLEDs.     

Paper‐Based Ratiometric Fluorescence Analytical Devices towards Point‐of‐Care Testing of Human Serum Albumin

Monitoring of human serum albumin (HSA) in a point‐of‐care fashion is urgently needed in particular for elderly or chronically ill patients. Herein, a dual‐state emissive chalcone probe having the feature of aggregation‐induced emission was designed and synthesized. The concentration of HSA can be evaluated by the ratios of emission from probes in aggregated and monomeric state, which gives a visually discernible red‐to‐green color change. A simple, portable paper‐based analytical device have been fabricated by integration of the recognition probe in the detection pad and employed for HSA test using the whole blood samples. This paper‐based assay shows the analytical capability comparable to the standard testing methods but is in a point‐of‐care fashion, providing a promising tool for at‐home HSA detection and HSA‐related disease diagnosis.     

Aggregation‐Induced Delayed Fluorescence Based on Donor/Acceptor‐Tethered Janus Carborane Triads: Unique Photophysical Properties of Nondoped OLEDs

Luminescent materials consisting of boron clusters, such as carboranes, have attracted immense interest in recent years. In this study, luminescent organic–inorganic conjugated systems based on o‐carboranes directly bonded to electron‐donating and electron‐accepting π‐conjugated units were elaborated as novel optoelectronic materials. These o‐carborane derivatives simultaneously possessed aggregation‐induced emission (AIE) and thermally activated delayed fluorescence (TADF) capabilities, and showed strong yellow‐to‐red emissions with high photoluminescence quantum efficiencies of up to 97 % in their aggregated states or in solid neat films. Organic light‐emitting diodes utilizing these o‐carborane derivatives as a nondoped emission layer exhibited maximum external electroluminescence quantum efficiencies as high as 11 %, originating from TADF.     

Luminescent Radical‐Excimer: Excited‐State Dynamics of Luminescent Radicals in Doped Host Crystals

The excited‐state dynamics of the photostable luminescent organic radical (3,5‐dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl (PyBTM) doped in a host crystal was investigated by using optically detected magnetic resonance (ODMR) and time‐resolved emission spectroscopies. In the radical system, the unpaired electron can be used as the probe for studying the electronic state and its dynamics. The mixed crystal with a high concentration of the radical showed excimer emission, together with the monomer emission. The ODMR signals were observed with opposite signs for monitoring the monomer and the excimer emissions. Based on their temperature and concentration dependencies, the excited‐state dynamics on the doped crystal and the mechanism of the excimer formation and the ODMR signal generation are discussed with the help of the quantum mechanical simulation of the excited‐state spin dynamics. The initial process of excimer formation has been clarified for the first time from the viewpoint of the spin‐dynamics.     

Photoluminescence Lifetime Imaging of Synthesized Proteins in Living Cells Using an Iridium–Alkyne Probe

Designing probes for real‐time imaging of dynamic processes in living cells is a continuous challenge. Herein, a novel near‐infrared (NIR) photoluminescence probe having a long lifetime was exploited for photoluminescence lifetime imaging (PLIM) using an iridium‐alkyne complex. This probe offers the benefits of deep‐red to NIR emission, a long Stokes shift, excellent cell penetration, low cytotoxicity, and good resistance to photobleaching. This example is the first PLIM probe applicable to the click reaction of copper(I)‐catalyzed azide–alkyne cycloaddition (CuAAC) with remarkable lifetime shifts of 414 ns, before and after click reaction. The approach fully eliminates the background interference and distinguishes the reacted probes from the unreacted probes, thus enabling the wash‐free imaging of the newly synthesized proteins within single living cells. Based on the unique properties of the iridium complexes, it is anticipated to have applications for imaging other processes within living cells.     

An Unexpected Chromophore–Solvent Reaction Leads to Bicomponent Aggregation‐Induced Phosphorescence

Organic luminogens with persistent room‐temperature phosphorescence (RTP) have found a wide range of applications. However, many RTP luminogens are prone to severe quenching in the crystalline state. Herein, we report a strategy to construct a donor‐sp³‐acceptor type luminogen that exhibits aggregation‐induced emission (AIE) while the donor‐sp²‐acceptor counterpart structure exhibits a non‐emissive solid state. Unexpectedly, it was discovered that a trace amount (0.01 %) of the structurally similar derivative, produced by a side reaction with the DMF solvent, could induce strong RTP with an absolute RTP yield up to 25.4 % and a lifetime of 48 ms, although the substance does not show RTP by itself. Single‐crystal XRD‐based calculations suggest that n–σ* orbital interactions as a result of structural similarity may be responsible for the strong RTP in the bicomponent system. This study provides a new insight into the design of multi‐component, solid‐state RTP materials from organic molecular systems.     

Tunable Dual Fluorescence of 3‐(2,2′‐Bipyridyl)‐Substituted Iminocoumarin

3‐(2,2′‐Bipyridyl)‐substituted iminocoumarin molecules (compounds 1 and 2 ) exhibit dual fluorescence. Each molecule has one electron donor and two electron acceptors that are in conjugation, which leads to fluorescence from two independent charge transfer (CT) states. To account for the dual fluorescence, we subscribe to a kinetic model in which both CT states form after rapid decays from the directly accessed S₁ and S₂ excited states. Due to the slow internal conversion from S₂ to S₁, or more likely the slow interconversion between the two subsequently formed CT states, dual emission is allowed to occur. This hypothesis is supported by the following evidence: 1) the emission at short and long ends of the spectrum originates from two different excitation spectra, which eliminates the possibility that dual emission occurs after an adiabatic reaction at the S₁ level. 2) The fluorescence quantum yield of compound 2 grows with increasing excitation wavelength, which indicates that the high‐energy excitation elevates the molecule to a weakly emissive state that does not internally convert to the low‐energy, highly emissive state. The intensity of the two emission bands of 1 is tunable through the specific interactions between either of the two electron acceptors with another species, such as Zn²⁺ in the current demonstration. Therefore, the development of ratiometric fluorescent indicators based on the dual‐emitting iminocoumarin system is conceivable. Further fundamental studies on this series of compounds using time‐resolved spectroscopic techniques, and explorations of their applications will be carried out in the near future.     

Aggregation‐Induced Delayed Fluorescence Luminogens for Efficient Organic Light‐Emitting Diodes

Aggregation‐induced delayed fluorescence (AIDF) can be regarded as a special case of aggregation‐induced emission (AIE). Luminogens with AIDF can simultaneously emit strongly in solid state and fully utilize the singlet and triplet excitons in organic light‐emitting diodes (OLEDs). In this work, two new AIDF luminogens, DMF‐BP‐DMAC and DPF‐BP‐DMAC, with an asymmetric D–A–D′ structure, are designed and synthesized. The characteristics of both luminogens are systematically investigated, including single crystal structures, theoretical calculations, photophysical properties and thermal stabilities. Inspired by their AIDF nature, the green‐emission non‐doped OLEDs based on them are fabricated, which afford good electroluminescence performances, with low turn‐on voltages of 2.8 V, high luminance of 52560 cd m^?2, high efficiencies of up to 14.4 %, 42.3 cd A^?1 and 30.2 lm W^?1, and very small efficiency roll‐off. The results strongly indicate the bright future of non‐doped OLEDs on the basis of robust AIDF luminogens.     

Ruthenium(II)–Polyimine–Coumarin Light‐Harvesting Molecular Arrays: Design Rationale and Application for Triplet–Triplet‐Annihilation‐Based Upconversion

Ru^II–bis‐pyridine complexes typically absorb below 450 nm in the UV spectrum and their molar extinction coefficients are only moderate (ε<16 000 M ^?1 cm^?1). Thus, Ru^II–polyimine complexes that show intense visible‐light absorptions are of great interest. However, no effective light‐harvesting ruthenium(II)/organic chromophore arrays have been reported. Herein, we report the first visible‐light‐harvesting Ru^II–coumarin arrays, which absorb at 475 nm (ε up to 63 300 M ^?1 cm^?1, 4‐fold higher than typical Ru^II–polyimine complexes). The donor excited state in these arrays is efficiently converted into an acceptor excited state (i.e., efficient energy‐transfer) without losses in the phosphorescence quantum yield of the acceptor. Based on steady‐state and time‐resolved spectroscopy and DFT calculations, we proposed a general rule for the design of Ru^II–polypyridine–chromophore light‐harvesting arrays, which states that the ¹IL energy level of the ligand must be close to the respective energy level of the metal‐to‐ligand charge‐transfer (M LCT) states. Lower energy levels of ¹IL/³IL than the corresponding ¹M LCT/³M LCT states frustrate the cascade energy‐transfer process and, as a result, the harvested light energy cannot be efficiently transferred to the acceptor. We have also demonstrated that the light‐harvesting effect can be used to improve the upconversion quantum yield to 15.2 % (with 9,10‐diphenylanthracene as a triplet‐acceptor/annihilator), compared to the parent complex without the coumarin subunit, which showed an upconversion quantum yield of only 0.95 %.     

A Light‐Up Probe with Aggregation‐Induced Emission for Real‐Time Bio‐orthogonal Tumor Labeling and Image‐Guided Photodynamic Therapy

Bio‐orthogonal tumor labeling is more effective in delivering imaging agents or drugs to a tumor site than active targeting strategy owing to covalent ligation. However, to date, tumor‐specific imaging through bio‐orthogonal labeling largely relies on body clearance to differentiate target from the intrinsic probe signal owing to the lack of light‐up probes for in vivo bio‐orthogonal labeling. Now the first light‐up probe based on a fluorogen with aggregation‐induced emission for in vivo bio‐orthogonal fluorescence turn‐on tumor labeling is presented. The probe has low background fluorescence in aqueous media, showing negligible non‐specific interaction with normal tissues. Once it reacts with azide groups introduced to tumor cells through metabolic engineering, the probe fluorescence is lightened up very quickly, enabling rapid tumor‐specific imaging. The photosensitizing ability was also used to realize effective image‐guided photodynamic tumor therapy.     

Fluorescence Study of Energy Transfer in PMMA Polymers with Pendant Oligo‐Phenylene‐Ethynylenes

A spectroscopic characterization of polymers containing rigid π‐conjugated oligo(phenyleneethynylene) chromophores as well as oligo(phenyleneethynylene) and methyl methacrylate is presented. The polymers exhibit molar masses of up to 15 000 g mol^?1 and a degree of polymerization between 22 and 80. Emission measurements of the monomeric and polymeric species show that radiative as well as nonradiative rates are influenced by the degree of polymerization due to intramolecular interactions of chromophores pendant to the polymer backbone. Time‐resolved emission anisotropy measurements suggest that energy migrates within the polymers. Steady‐state emission anisotropy measurements also point to energy migration. Additionally, two oligo(phenyleneethynylene)s with different sizes of the conjugated system are copolymerized in order to enable energy trapping due to energy transfer. The shortened energy‐donor fluorescence lifetime within the donor–acceptor copolymers suggest energy transfer. Depending on the degree of polymerization, dispersion of the donor fluorescence lifetime is observed.     

Bridged Stilbenes: AIEgens Designed via a Simple Strategy to Control the Non‐radiative Decay Pathway

To broaden the application of aggregation‐induced emission (AIE) luminogens (AIEgens), the design of novel small‐molecular dyes that exhibit high fluorescence quantum yield (Φ_fl) in the solid state is required. Considering that the mechanism of AIE can be rationalized based on steric avoidance of non‐radiative decay pathways, a series of bridged stilbenes was designed, and their non‐radiative decay pathways were investigated theoretically. Bridged stilbenes with short alkyl chains exhibited a strong fluorescence emission in solution and in the solid state, while bridged stilbenes with long alkyl chains exhibited AIE. Based on this theoretical prediction, we developed the bridged stilbenes BPST[7] and DPB[7], which demonstrate excellent AIE behavior.