Induction of Strong Long‐Lived Room‐Temperature Phosphorescence of N‐Phenyl‐2‐naphthylamine Molecules by Confinement in a Crystalline Dibromobiphenyl Matrix

The design and preparation of metal‐free organic materials that exhibit room‐temperature phosphorescence (RTP) is a very attractive topic owing to potential applications in organic optoelectronic devices. Herein, we present a facile approach to efficient and long‐lived organic RTP involving the doping of N‐phenylnaphthalen‐2‐amine (PNA) or its derivatives into a crystalline 4,4′‐dibromobiphenyl (DBBP) matrix. The resulting materials showed strong and persistent RTP emission with a quantum efficiency of approximately 20 % and a lifetime of a few to more than 100 milliseconds. Bright white dual emission containing blue fluorescence and yellowish‐green RTP from the PNA‐doped DBBP crystals was also confirmed by Commission Internationale de l'Eclairage (CIE) coordinates of (x=0.29–0.31, y=0.38–0.41).     

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.     

Crystallization-induced phosphorescence of pure organic luminogens

This review summarizes the recent progress of efficient room temperature phosphorescence (RTP) from pure organic luminogens achieved by crystallization-induced phosphorescence (CIP), with focus on the advances in our group. Besides homocrystals, mixed crystals and cocrystals are also discussed. Meanwhile, intriguing RTP emission from the luminogens without conventional chromophores is demonstrated.     

Crystal‐State Photochromism and Dual‐Mode Mechanochromism of an Organic Molecule with Fluorescence,Room‐Temperature Phosphorescence,and Delayed Fluorescence

A D‐A‐D′ type pure organic molecule, named ODFRCZ, has unique triple‐emission character covering fluorescence, phosphorescence, and delayed fluorescence (DF). The phosphorescence of ODFRCZ has a rather long lifetime of about 350 ms at room temperature. One dimer of ODFRCZ with enhanced parallel molecular packing acts more effectively to prompt ISC processes, which further generates room‐temperature phosphorescence (RTP), owing to the larger transition dipole moment and closer energy level between S₁ and T_n. ODFRCZ is a rare example of an organic RTP molecule that shows dual‐stimuli responsiveness of dual‐mode mechanochromism (fluorescence red‐shift and RTP/DF on‐off switch) and reversible crystal‐state photochromism. This work may broaden the knowledge for stimuli‐responsive RTP organic molecules and lay the foundation for their wide‐scale applications.     

Crystal‐State Photochromism and Dual‐Mode Mechanochromism of an Organic Molecule with Fluorescence,Room‐Temperature Phosphorescence,and Delayed Fluorescence

A D‐A‐D′ type pure organic molecule, named ODFRCZ, has unique triple‐emission character covering fluorescence, phosphorescence, and delayed fluorescence (DF). The phosphorescence of ODFRCZ has a rather long lifetime of about 350 ms at room temperature. One dimer of ODFRCZ with enhanced parallel molecular packing acts more effectively to prompt ISC processes, which further generates room‐temperature phosphorescence (RTP), owing to the larger transition dipole moment and closer energy level between S₁ and T_n. ODFRCZ is a rare example of an organic RTP molecule that shows dual‐stimuli responsiveness of dual‐mode mechanochromism (fluorescence red‐shift and RTP/DF on‐off switch) and reversible crystal‐state photochromism. This work may broaden the knowledge for stimuli‐responsive RTP organic molecules and lay the foundation for their wide‐scale applications.     

Blue‐emitting poly[(m‐phenylene vinylene)‐alt‐(o‐phenylene vinylene)]s: The effect of regioregularity on the optical properties

Poly[(m‐phenylene vinylene)‐alt‐(o‐phenylene vinylene)]s with different contents of cis‐/trans‐CH?CH ( 3 and 6 ) have been synthesized through Wittig condensation. The polymers exhibit good solubility in common organic solvents such as toluene and tetrahydrofuran. A comparison of the optical properties has been made between 3 and its phenyl regioisomers containing either p‐phenylene or m‐phenylene units. The results show that the regiochemistry of the phenyl ring can be a useful tool for tuning the emission color of π‐conjugated polymers because the extension of π conjugation can only partially be achieved through an o‐phenylene bridge. Although both polymers 3 and 6 exhibit comparable low fluorescence quantum efficiencies (≈0.18) in solution, their films are highly luminescent, showing a broad emission band near 456 nm (blue color). Electroluminescence results show that the device of polymer 3 , which has a higher content of trans‐CH?CH linkages, is about 20 times more efficient than that of 6 . © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2650–2658, 2003     

Crystallization-induced phosphorescence,remarkable mechanochromism,and grinding enhanced emission of benzophenone-aromatic amine conjugates

Twisted pure organic luminogens based on benzophenone and aromatic amines exhibit both fluorescence and phosphorescence in crystals, while owning merely red-shifted fluorescence at ground amorphous solids. Some of them even demonstrate greatly enhanced emission upon grinding.     

Designing Efficient and Ultralong Pure Organic Room‐Temperature Phosphorescent Materials by Structural Isomerism

Pure organic materials with ultralong room‐temperature phosphorescence (RTP) are attractive alternatives to inorganic phosphors. However, they generally show inefficient intersystem crossing (ISC) owing to weak spin–orbit coupling (SOC). A design principle based on the realization of small energy gap between the lowest singlet and triplet states (ΔE_ST) and pure ππ* configuration of the lowest triplet state (T₁) via structural isomerism was used to obtain efficient and ultralong RTP materials. The meta isomer of carbazole‐substituted methyl benzoate exhibits an ultralong lifetime of 795.0 ms with a quantum yield of 2.1 %. Study of the structure–property relationship shows that the varied steric and conjugation effects imposed by ester substituent at different positions are responsible for the small ΔE_ST and pure ππ* configuration of T₁.     

A New Approach to Prepare Efficient Blue AIE Emitters for Undoped OLEDs

Two aggregation‐induced emission active luminogens (TPE–pTPA and TPE–mTPA) were successfully synthesized. For comparison, another six similar compounds were prepared. Because of the introduced hole‐dominated triphenylamine (TPA), fluorene groups with high luminous efficiency, and unconjugated linkages, the π conjugation length of the obtained luminogens is effectively restricted to ensure their blue emission. The undoped organic light‐emitting diodes based on TPE–pTPA and TPE–mTPA exhibited blue or deep‐blue emissions, low turn‐on voltages (3 V), and high electroluminescence efficiencies with L_max, η_C,max, and η_P,max values of up to 26 697 cd m^?2, 3.37 cd A^?1, and 2.40 Lm W^?1.     

Room temperature phosphorescence from organic luminogens in“non-crystalline” state

ABSTRACT

The field of room temperature phosphorescence (RTP) from purely organic materials has made rapid strides in recent years primarily due to its tremendous promise in the areas of photovoltaics, photocatalysis, bioimaging, sensing, etc. Although, the RTP properties, at one time, were considered to be exclusive features of organometallic and inorganic phosphors, a great progress in the molecular design coupled with a much better understanding of the triplet state stabilisation has led to the creation of a plethora of organic RTP materials in the current decade. In this focussed review, a special category of organic luminogens which, rather remarkably, exhibit efficient RTP emission in amorphous or fluidic state is discussed. A few selected examples of such ‘non-crystalline’ organic RTP luminogens are highlighted with an emphasis on the basic design principles and the strategies to increment the phosphorescence efficiency.     

Mechanoluminescence or Room‐Temperature Phosphorescence: Molecular Packing‐Dependent Emission Response

Mechanoluminescence (ML) and room‐temperature photophosphorescence (RTP) were achieved in polymorphisms of a triphenylamine derivative with ortho‐substitution. This molecular packing‐dependent emission afforded crucial information to deeply understand the intrinsic mechanism of different emission forms and the possible packing–function relationship. With the incorporation of solid‐state ¹³C NMR spectra of single crystals, as well as the analysis of crystal structures, the preferred packing modes for ML and/or RTP were investigated in detail, which can guide the reasonable design of organic molecules with special light‐emission properties.     

Accessing Tunable Afterglows from Highly Twisted Nonaromatic Organic AIEgens via Effective Through‐Space Conjugation

Nonaromatic, cross‐conjugated, and highly twisted luminogens consisting of acylated succinimides demonstrate aggregation‐induced emission characteristics along with tunable multicolor photoluminescence and afterglows in their single crystals. Effective through‐space conjugation among different moieties bearing n/π electrons promote the spin–orbit coupling and intersystem crossing and lead to diverse emissive clusters with concurrently rigidified conformations, thus allowing readily tunable emissions. Derived from it, the proof‐of‐concept application for advanced anti‐counterfeiting is illustrated. These results should spur the rational design of novel nonaromatic AIEgens, and moreover advance understandings of the non‐traditional intrinsic luminescence and the origin of tunable multicolor afterglows.     

Transition‐Metal‐Catalyzed Cyanation by Using an Electrophilic Cyanating Agent,N‐Cyano‐N‐phenyl‐p‐toluenesulfonamide (NCTS)

The ability to introduce a nitrile group into a biologically active compound is very useful in organic synthesis, owing to the importance of nitrile groups in transformations and tuning molecular properties. To date, nucleophilic cyanation has been the most used strategy for this purpose, whilst electrophilic cyanation reactions are less developed. Recently, the electrophilic cyanation reagent N‐cyano‐N‐phenyl‐p‐toluenesulfonamide (NCTS) has received increasing attention, owing to its superior properties in terms of safety and practicality. This Focus Review summarizes recent progress in transition‐metal‐catalyzed cyanation reactions that use NCTS.     

Crystallization-induced phosphorescence of benzils at room temperature

Efficient room temperature phosphorescence (RTP) is rarely observed in pure organic luminogens. However, we have newly observed that benzil and its derivatives are nonluminescent in solvents and thin layer chromatography (TLC) plates, but become highly phosphorescent in crystal state at room temperature, exhibiting typical crystallization-induced phosphorescence (CIP) characteristics. The CIP phenomenon is ascribed to the restriction of intramolecular rotations in crystals owing to effective intermolecular interactions. Such intermolecular interactions greatly rigidify the molecular conformation and significantly decrease the nonradiative deactivation channels of the triplet excitons, thus giving boosted phosphorescent emission at room temperature.     

Complex‐radical terpolymerization of acceptor–donor–acceptor systems: Maleic anhydride (n‐butyl methacrylate)–styrene–acrylonitrile

Some features of radical ternary copolymerization of maleic anhydride (MA)–styrene (St)–acrylonitrile (AN) and n‐butyl methacrylate (BMA)–St–AN acceptor–donor–acceptor monomer systems have been revealed. The terpolymer compositions and kinetics of copolymerizations were studied in the initial and high conversion stages. The considerable divergence in the copolymer compositions was observed when a strong acceptor MA monomer was substituted with BMA having comparatively low acceptor character in the ternary system studied. Obtained results show that terpolymerization proceeded mainly through “complex” mechanism in the state of near binary copolymerization of St…MA (or BMA) and AN…St complexes only in the chosen ratios of complexed monomers. The terpolymers synthesized have high thermal stabilities (295–325 °C), which is explained by possible intermolecular fragmentation of AN‐units through cyclization and crosslinking reactions during thermotreatment in the isothermal heating conditions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2652–2662, 2000     

Engineering the Interconnecting Position of Star‐Shaped Donor–π–Acceptor Molecules Based on Triazine,Spirofluorene, and Triphenylamine Moieties for Color Tuning from Deep Blue to Green

Pi‐conjugated organic molecules featuring the donor–bridge–acceptor (D–π–A) structure have been widely used in semiconducting materials owing to their rigid structure, good thermal stability, excellent charge transfer, and high emission efficiency. To investigate the effect of the D–π–A molecular structure on the photophysical properties, in this contribution, three star‐shaped D–π–A isomers based on the 2,4,6‐triphenyl‐1,3,5‐triazine, spirofluorene, and triphenylamine moieties, that is, p‐TFTPA, mp‐TFTPA, and m‐TFTPA, were synthesized by elaborately engineering the interconnecting position in the building‐block units. The optophysical properties of these compounds were systematically explored by experiments and theory calculations. Definitively, changing the interconnecting position in these molecules played a significant role in the degree of π conjugation, which resulted in tunable emission colors from deep blue to green. Moreover, these isomers were employed as emissive dopants in organic light‐emitting diodes. The highest external quantum efficiency of 2.3 % and current efficiency of 6.2 cd A^?1 were achieved by using the p‐TFTPA based device. This research demonstrates a feasible way to realize blue emitters by engineering D–π–A conjugation.     

Visible‐Light‐Excited Room‐Temperature Phosphorescence in Water by Cucurbit[8]uril‐Mediated Supramolecular Assembly

Solid‐state materials with efficient room‐temperature phosphorescence (RTP) emissions have found widespread applications in materials science, while liquid or solution‐phase pure organic RTP emission systems has been rarely reported, because of the nonradiative decay and quenchers from the liquid medium. Reported here is the first example of visible‐light‐excited pure organic RTP in aqueous solution by using a supramolecular host‐guest assembly strategy. The unique cucurbit[8]uril‐mediated quaternary stacking structure allows tunable photoluminescence and visible‐light excitation, enabling the fabrication of multicolor hydrogels and cell imaging. The present assembly‐induced emission approach, as a proof of concept, contributes to the construction of novel metal‐free RTP systems with tunable photoluminescence in aqueous solution, providing broad opportunities for further applications in biological imaging, detection, optical sensors, and so forth.     

A gelable pure organic luminogen with fluorescence-phosphorescence dual emission

Pure organic luminogens with room temperature phosphorescence(RTP) have drawn much attention due to their fundamental importance and promising applications in optoelectronic devices, bioimaging, sensing, etc. Fluorescence-phosphorescence dual emission at room temperature, however, is rarely observed in pure organic materials. Herein, we reported a metal-and heavy-atom free pure organic luminogen with tert-butyl groups, DtBuCZBP, which is ready to form organogels in dimethylsulfoxide(DMSO).It emits prompt and delayed fluorescence, as well as RTP, namely dual emission in as-prepared solid, gels and polymeric films.To the best of our knowledge, it is the first example of metal-and heavy-atom free pure organic gelator with RTP emission. Such unique RTP and moreover dual emission properties in different states make DtBuCZBP a potential material for diverse applications.     

Double D–π–A Dye Linked by 2,2′‐Bipyridine Dicarboxylic Acid: Influence of para‐ and meta‐Substituted Carboxyl Anchoring Group

Starting from 2,2′‐bipyridine dicarboxylic acid, two new (D –π–A)₂ sensitizers, including m‐DA with the carboxyl anchoring group substituted meta to the donor‐bridge moiety and p‐DA with a para‐substituted anchoring group, were synthesized in order to evaluate the impact of the position of the anchoring group on the optical, electrochemical, and photovoltaic properties of dye‐sensitized solar cells. p‐DA exhibits red‐shifted absorption behavior compared to m‐DA, owing to the more efficiently extended π‐conjugation with para substitution. Both m‐DA and p‐DA are adsorbed on the mesoporous TiO₂ surface by using both of their carboxylic acid groups in a bianchoring mode, which is confirmed through attenuated total reflectance FTIR analysis. Red‐shifted absorption of p‐DA assists the achievement of a red‐shifted incident photon‐to‐electron conversion efficiency and a higher short‐circuit current density than m‐DA. The photogenerated electron lifetime in TiO₂ is also found to be higher for para substituted p‐DA than the meta‐substituted m‐DA, which results in a higher open‐circuit voltage. All of the results suggest that dicarboxyl‐2,2′‐bipyridine can be used as an acceptor for metal‐free organic sensitizers. However, the anchoring segments should be adjusted to the favorable position of the corresponding donor‐bridge moieties for better conjugation.     

Synthesis of alkaline‐developable,photosensitive hyperbranched polyimides through the reaction of carboxylic acid dianhydrides and trisamines

Hyperbranched polyimides (HBPI)s with high glass‐transition temperatures and excellent thermal stability were synthesized through the reaction of commercially available carboxylic acid dianhydrides with tris[4‐(4‐aminophenoxy)phenyl]ethane (TAPE). In particular, hyperbranched polyimide HBPI(TAPE‐DSDA), prepared through the reaction of TAPE with 3,3′,4,4′‐diphenylsulfonetetracarboxylic dianhydride (DSDA), showed higher thermal stability and good solubility. Furthermore, alkaline‐developable, photosensitive HBPI(TAPE‐DSDA)‐MA‐CA was prepared through the reaction of HBPI(TAPE‐DSDA) with glycidyl methacrylate with tetrabutylammonium bromide as a catalyst in N‐methyl‐2‐pyrrolidinone (NMP) followed by the addition reaction of cis‐1,2,3,6‐tetrahydrophthalic anhydride with triphenylphosphine as a catalyst in NMP. The glass‐transition temperatures of HBPI(TAPE‐DSDA)‐MA‐CA were greater than 300 °C. A resist composed of 74 wt % HBPI(TAPE‐DSDA)‐MA‐CA, 22.2 wt % trimethylpropane triacrylate, and 3.8 wt % Irgacure 907 as a photoinitiator achieved a resolution of a 55‐μm line pattern and a 275‐μm space pattern by UV irradiation (1000 mJ/cm²). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3697–3707, 2004