Crystallization-induced Phosphorescence Research Articles

A Facile One-Step Self-Assembly Strategy for Novel Carbon Dots Supramolecular Crystals with Ultralong Phosphorescence Controlled by NH4.

A new methodological design is proposed for carbon dots (CDs)-based crystallization-induced phosphorescence (CIP) materials via one-step self-assembled packaging controlled by NH4 +. O-phenylenediamine (o-PD) as a nitrogen/carbon source and the ammonium salts as oxidants are used to obtain CDs supramolecular crystals with a well-defined staircase-like morphology, pink fluorescence and ultralong green room-temperature phosphorescence (RTP) (733.56ms) that is the first highest value for CDs-based CIP materials using pure nitrogen/carbon source by one-step packaging. Wherein, NH4 + and o-PD-derived oxidative polymers are prerequisites for self-assembled crystallization so as to receive the ultralong RTP. Density functional theory calculation indicates that NH4 + tends to anchor to the dimer on the surface state of CDs and guides CDs to cross-arrange in an X-type stacking mode, leading to the spatially separated frontier orbitals and the through-space charge transfer (TSCT) excited state in turn. Such a self-assembled mode contributes to both the small singlet-triplet energy gap (ΔEST) and the fast inter-system crossing (ISC) process that is directly related to ultralong RTP. This work not only proposes a new strategy to prepare CDs-based CIP materials in one step but also reveals the potential for the self-assembled behavior controlled by NH4 +.

Side group dependent room temperature crystallization-induced phosphorescence of benzil based all organic phosphors.

In this work, we report alkoxy substituted benzil based all organic room temperature phosphors which showed crystallization induced phosphorescence (CIP). Nine title compounds were prepared with various alkyl lengths (OCnH2n+1: n = 8-16) and the effect of alkyl side group length on the phosphorescence performance was investigated, as compared to p-anisil. It was found that both phosphorescence quantum yield and lifetime increased concomitantly as the alkyl length increased up to nonyloxy (BZL-OC9). Further increase in the carbon number caused the phosphorescence performance to deteriorate due to greater conformational freedom of the side groups. An incredible quantum yield of 70% was achieved for BZL-OC9. A promising finding is that the increased quantum yield was accompanied by the increase in the lifetime relative to p-anisil, which has been historically challenging. Single crystallography coupled with UV-Vis spectroscopy revealed that a higher level of intermolecular π-π interactions was observed from p-anisil while more alkyl interactions with less intermolecular π-orbital overlap were found for BZL-OC8. As a result, molecular rigidification with less phosphorescence quenching was achieved for BZL-OC8 leading to enhanced performance. A precipitation study on a dichloromethane solution as a function of the content of MeOH (poor solvent) proved that the emission of the BZL-OCn system is truly aggregation-induced. The current work demonstrates that strategic side group engineering could be a promising approach to developing high-performance all organic phosphors as well as improving the properties of existing phosphors.

Aqueous solutions with information on solids: room-temperature phosphorescence of polysaccharide-benzophenone complexes.

Benzophenone and its derivatives emit crystallization-induced phosphorescence despite their simple structures. To easily modify their phosphorescence properties, we prepared phosphorescence-emitting aqueous solutions of polysaccharide-benzophenone and polysaccharide-4,4'-difluorobenzophenone complexes, which exhibit excellent biocompatibility and biodegradability.

Recent Advances in Organic Room-Temperature Phosphorescence of Heteroatom (B/S/P)-Containing Chromophores

Recent Advances in Organic Room-Temperature Phosphorescence of Heteroatom (B/S/P)-Containing Chromophores

Tunable Photoluminescence Properties of Cotton Fiber With Gradually Changing Crystallinity.

The alkali mercerizing process of semicrystalline cotton fiber (CF) is widely used in the printing and dyeing industry. The crystallinity change in the mercerizing process has been studied and certain laws have been obtained, but there is still a certain distance between the theoretical research results and the practical applications. CF is almost composed of cellulose, combined with the photoluminescence (PL) phenomenon of cellulose; herein, the varying crystallinity is correlated with its PL behavior after being treated with different concentrations of NaOH. In line with the characteristics of nonconventional luminogens, CF enjoys excitation-dependent emission and persistent room temperature phosphorescence (p-RTP) behavior. The emission spectra of all samples under the same excitation wavelength indicate that the change of CF crystallinity has a significant impact on its fluorescence and p-RTP emission. As the concentration of NaOH increases, the varying trend of quantum efficiency (QY) is consistent with the changed crystallinity of CF. Interestingly, the lifetime of p-RTP is exactly the opposite of the crystallinity change law. Clustering-triggered emission (CTE), crystallization-Induced Phosphorescence (CIP) mechanism, and the swelling due to hydrated sodium ions can reasonably explain these interesting photophysical processes, which also can be supported by theoretical calculations. The above studies have basically clarified the inherent law between the crystalline change of CF and the PL emission behavior during the alkali treatment process, which can be used as a theoretical reference for real-time monitoring of CF crystallinity changes using the spectral method in the actual cotton mercerizing process.

Novel D-A chromophores with condensed 1,2,4-triazine system simultaneously display thermally activated delayed fluorescence and crystallization-induced phosphorescence.

Control of photophysical properties is crucial for the continued development of electroluminescent devices and luminescent materials. Preparation and study of original molecules uncovers design rules towards efficient materials and devices. Here we have prepared 7 new compounds based on the popular donor-acceptor design used in thermally activated delayed fluorescence emitters. We introduce for the first time benzofuro[3,2-e]-1,2,4-triazine and benzothieno[3,2-e]-1,2,4-triazine acceptors which were connected to several common donors: phenoxazine, phenothiazine, carbazole and 3,6-di-tert-butylcarbazole. DFT calculations, and steady-state and time-resolved photophysical studies were conducted in solution and in solid states. While derivatives with azine moieties are non-emissive in any form, the compounds comprising 3,6-di-tert-butylcarbazole display TADF in all cases. More interestingly, the two derivatives substituted with a carbazole donor are TADF active when dispersed in a polymer matrix and phosphorescent at room temperature in neat films (microcrystalline form).

Ben Zhong Tang.

"The most exciting thing about my research is the joy of making the impossible possible. My biggest motivation is curiosity (to explore the unknown) and satisfaction (of blazing a trail) …" Find out more about Ben Zhong Tang in his Author Profile.

Crystallization-Induced Red Phosphorescence and Grinding-Induced Blue-Shifted Emission of a Benzobis(1,2,5-thiadiazole)-Thiophene Conjugate.

Mechanochromic luminogens are of significant importance in both academic and technical aspects. Thus far, most mechanochromic compounds exhibit bathochromically shifted emission upon grinding; the examples of those that exhibit blue-shifted emission still remain limited. Herein, a donor–acceptor–donor (D–A–D)-structured conjugate, namely 4,7-di(2-thienyl)-2,1,3-benzothiadiazole (DTBT), comprising benzobis(1,2,5-thiadiazole) and thiophene units, has been carefully synthesized and investigated. DTBT exhibits typical intramolecular charge transfer (ICT) characteristics, crystallization-induced phosphorescence (CIP), and remarkable mechanochromism. Although it merely emits fluorescence in solutions with distinct ICT features, its crystals demonstrate bright-red room-temperature phosphorescence (616 nm) with efficiency up to 25.0% and generate yellow excimer fluorescence (578 nm) upon mechanical grinding, accompanying decreased lifetimes from 10.9 μs to 3.5 ns and a blue-shifted emission of 38 nm. These results highly indicate the feasibility to fabricate novel CIP luminogens with blue-shifted mechanochromism.

A simple and efficient phosphorescent probe for iodide-specific detection based on crystallization-induced phosphorescence of organic ionic crystals

A novel time-gated detection method for iodide ions based on the unique crystallization-induced phosphorescence of tetraphenylphosphonium iodide was developed.

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

Pure organic luminogens with efficient room temperature phosphorescence (RTP) and remarkable mechanochromism are highly desired in view of their fundamental significance and technical applications. Herein, four twisted pure organic luminogens based on benzophenone and aromatic amines were synthesized and their photophysical properties were thoroughly investigated. They exhibit crystallization-induced phosphorescence (CIP), giving bright fluorescence and phosphorescence dual emission in crystals. Upon grinding, they become amorphous and emit predominantly red-shifted fluorescence, demonstrating remarkable mechanochromism. Furthermore, three of them even demonstrate greatly enhanced emission upon grinding, which is rarely observed in twisted D-A structured luminogens.

Effects of aromatic core and flexible terminal chain structures on the properties of luminous liquid-crystalline gold(i) complexes for functional materials

ABSTRACTLuminescent liquid-crystalline (LC) Au complexes with various aromatic cores and flexible terminal chains were synthesized. The aromatic core aspect ratio crucially affected the LC temperature range and melting point of the complexes. Moreover, branched flexible chains reduced the melting point, thus expanding the LC temperature range. In the crystalline and LC phases of the complexes, fluorescence was quenched by the aggregation-caused quenching effect, but phosphorescence was enhanced by the crystallization-induced phosphorescence effect. However, no phosphorescence was observed in the isotropic phase. Thus, not only aggregation but also regularity of molecular aggregates is necessary for the observed crystallization-induced phosphorescence effect.

ChemInform Abstract: Crystallization‐Induced Phosphorescence of Pure Organic Luminogens

AbstractReview: [30 refs.

Crystallization-induced phosphorescence of pure organic luminogens

Abstract 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.

Achieving Persistent Room Temperature Phosphorescence and Remarkable Mechanochromism from Pure Organic Luminogens.

Persistent room temperature phosphorescence (RTP) from pure organic luminogens can be rationally realized based on the crystallization-induced phosphorescence phenomenon and severe crystallization. A perfect crystal with dense molecular packing and effective inter-molecular interactions isolates the triplet excitons from quenching sites and significantly blocks the high-energy vibrational dissipation, thus yielding long-lasting RTP.

Tuning the singlet-triplet energy gap of AIE luminogens: crystallization-induced room temperature phosphorescence and delay fluorescence, tunable temperature response, highly efficient non-doped organic light-emitting diodes.

In this contribution, we finely tuned the singlet-triplet energy gap (ΔEST) of AIE-active materials to modulate their fluorescence, phosphorescence and delay fluorescence via rational molecular design and investigated the possible ways to harvest their triplet energy in OLEDs. Noteworthily, two molecules o-TPA-3TPE-o-PhCN and o-TPA-3TPE-p-PhCN with larger ΔEST values (0.59 eV and 0.45 eV, respectively) emitted efficient long-lived low temperature phosphorescence in their glassy solutions and exhibited efficient crystallization-induced room temperature phosphorescence (RTP). Meanwhile, it was the first time to observe a novel crystallization-induced delay fluorescence phenomenon in another AIE-active molecule p-TPA-3TPE-p-PhCN owing to its very small ΔEST value (0.21 eV). It was also found that molecules with various ΔEST values showed significantly different temperature sensitivity. Non-doped electroluminescent (EL) devices using these molecules as light-emitting layers were fabricated, exhibiting external quantum efficiencies (EQE) higher than theoretical values of purely singlet emitter type devices. Particularly, p-TPA-3TPE-p-PhCN showed outstanding device performances with high luminance and efficiencies up to 36,900 cd m(-2), 11.2 lm W(-1), 12.8 cd A(-1) and 4.37%, respectively, considering that its solid-state quantum yield was only 42%. All the above observations suggested that tuning the ΔEST values of AIE materials is a powerful methodology to generate many more interesting and meaningful optoelectronic properties.

Room temperature phosphorescence from natural products: Crystallization matters

Efficient room temperature phosphorescence is observed in natural compounds and polymers such as starch, cellulose, bovine serum albumin (BSA), and some other carbohydrates. Whereas being practically nonluminescent in solutions and TLC plates, they emit bright phosphorescence in the crystalline states with lifetime up to microseconds, exhibiting crystallization-induced phosphorescence (CIP) characteristics. The CIP of these natural products without any conventional chromophores offers a new platform for the exploration of conceptually novel luminogens.

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.

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.

Room temperature phosphorescence from natural products: Crystallization matters

Efficient room temperature phosphorescence is observed in natural compounds and polymers such as starch, cellulose, bovine serum albumin (BSA), and some other carbohydrates. Whereas being practically nonluminescent in solutions and TLC plates, they emit bright phosphorescence in the crystalline states with lifetime up to microseconds, exhibiting crystallization-induced phosphorescence (CIP) characteristics. The CIP of these natural products without any conventional chromophores offers a new platform for the exploration of conceptually novel luminogens.

Crystallization-Induced Phosphorescence of Pure Organic Luminogens at Room Temperature

Phosphorescence has rarely been observed in pure organic chromophore systems at room temperature. We herein report efficient phosphorescence from the crystals of benzophenone and its derivatives with a general formula of (X-C6H4)2C═O (X = F, Cl, Br) as well as methyl 4-bromobenzoate and 4,4′-dibromobiphenyl under ambient conditions. These luminogens are all nonemissive when they are dissolved in good solvents, adsorbed on TLC plates, and doped into polymer films, because active intramolecular motions such as rotations and vibrations under these conditions effectively annihilate their triplet excitons via nonradiative relaxation channels. In the crystalline state, the intramolecular motions are restricted by the crystal lattices and intermolecular interactions, particularly C−H···O, N−H···O, C−H···X (X = F, Cl, Br), C−Br···Br−C, and C−H···π hydrogen bonding. The physical constraints and multiple intermolecular interactions collectively lock the conformations of the luminogen molecules. This structural rigidification effect makes the luminogens highly phosphorescent in the crystalline state at room temperature.