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

Purely organic room-temperature phosphors,which have received extensive attention as emerging stateof-the-art luminescent materials in various fields,have a longer lifetime than fluorophores.The energy gap law and El-Sayed’s rule provide clear design principles for the development of organic room-temperature phosphorescence.Therefore,the incorporation of heteroatoms(such as sulfur and phosphorus)usually promotes the intersystem crossing rate and increases the 3(π,π*)configuration to realize long lifetimes.Furthermore,boron-containing phosphors not only display excellent phosphorescence properties but also expand El-Sayed’s rule without(n,π*)transitions.This review summarizes recent work on organic phosphorescence of heterocycles with boron,sulfur,and phosphorus heteroatoms and highlights the significance of the guidelines for constructing efficient phosphorescence molecules.This work is instrumental in further diversifying the pool of phosphorescent molecules and developing new and effective design strategies.

Recent Advances in Pure-Organic Host-Guest Room-Temperature Phosphorescence Systems Toward Bioimaging

Organic room-temperature phosphorescence(RTP)materials have garnered considerable attention in the fields of biosensing,optoelectronic devices,and anticounterfeiting because of their substantial Stokes shifts,tunable emission wavelengths,and prolonged lifetimes.These materials offer remarkable advantages for biological imaging applications by effectively reducing environmental autofluorescence and enhancing imaging resolution.Recently,host-guest systems have been employed as efficient approaches to fabricate pure-organic RTP materials for bioimaging,providing benefits such as controllable preparation and flexible modulation.Consequently,an increasing number of corresponding studies are being reported;however,a comprehensive systematic review is still lacking.Therefore,we summarize recent advances in the development of pureorganic RTP materials using host-guest systems with regard to bioimaging,including rigid matrices and sensitization.The challenge and potential of RTP for biological imaging are also proposed to promote the biomedical applications of organic RTP materials with excellent optical properties.

A facile and green strategy to obtain organic room-temperature phosphorescence from natural lignin

Seeking pure organic functional luminescent materials that are processed from green, low-cost, and sustainable resources remains a challenging but beneficial task. As an abundant natural polymer composed of crosslinked phenol ether units, lignin is a potential source of organic luminescent material because of the presence of extensive aromatic fragments. In the present work, a remarkable afterglow involving room-temperature phosphorescence(RTP) was achieved via simply embedding alkalized lignin into polyvinyl alcohol(PVA) matrix, and an ultralong luminescence lifetime of more than 160 ms was observed. More importantly, our study revealed that small fragments of hydrolyzed lignin(named LA-H) bearing extensive phenolic oxygen anions were the effective luminescent species. When embedded into a PVA matrix, LA-H showed remarkably high luminescence quantum yield and long lifetime of RTP emission compared with those of unprocessed lignin. Additionally, the various phenol oxygen anion moieties endowed LA-H with an excitation-dependent characteristic: the color-tunable RTP could be simply tuned from a maximum emission wavelength of 434–532 nm via altering the excitation wavelength. Thus, the color-tunable afterglow of emissive LA-H could be facilely obtained with a yield up to 38.4% using simple acid hydrolysis of lignin without other complex synthesis procedures. This work opens new avenues in the large-scale preparation of low-cost and sustainable pure organic RTP materials.

Ultralong organic room-temperature phosphorescence of electrondonating and commercially available host and guest molecules through efficient Förster resonance energy transfer

Ultralong organic room-temperature phosphorescence(RTP)materials have attracted tremendous attention recently due to their diverse applications.Several ultralong organic RTP materials mimicking the host-guest architecture of inorganic systems have been exploited successfully.However,complicated synthesis and high expenditure are still inevitable in these studies.Herein,we develop a series of novel host-guest organic phosphorescence systems,in which all luminophores are electron-rich,commercially available and halogen-atom-free.The maximum phosphorescence efficiency and the longest lifetime could reach 23.6%and 362 ms,respectively.Experimental results and theoretical calculation indicate that the host molecules not only play a vital role in providing a rigid environment to suppress non-radiative decay of the guest,but also show a synergistic effect to the guest through Förster resonance energy transfer(FRET).The commercial availability,facile preparation and unique properties also make these new host-guest materials an excellent candidate for the anti-counterfeiting application.This work will inspire researchers to develop new RTP systems with different wavelengths from commercially available luminophores.

Red-Emissive Organic Room-Temperature Phosphorescence Material for Time-Resolved Luminescence Bioimaging

Organic room-temperature phosphorescence(RTP)materials have been used in high-resolution imaging.However,the development of long-wavelength-emis sion RTP materials in aqueous solution remains a challenge.Here,we report red-emissive RTP materials via integration of the ring-fusing effect and host–guest interaction.

Effect of aggregation on thermally activated delayed fluorescence and ultralong organic phosphorescence:QM/MM study

Aggregation-induced thermally activated delayed fluorescence(TADF)phenomena have attracted extensive attention recently.In this paper,several theoretical models including monomer,dimer,and complex are used for the explanation of the luminescent properties of(R)-5-(9H-carbazol-9-yl)-2-(1,2,3,4-tetrahydronaphthalen-1-yl)isoindoline-1,3-dione((R)-ImNCz),which was recently reported[Chemical Engineering Journal 418129167(2021)].The polarizable continuum model(PCM)and the combined quantum mechanics and molecular mechanics(QM/MM)method are adopted in simulation of the property of the molecule in the gas phase,solvated in acetonitrile and in aggregation states.It is found that large spin–orbit coupling(SOC)constants and a smaller energy gap between the first singlet excited state and the first triplet excited state(△E_(st))in prism-like single crystals(SC_(p)-form)are responsible for the TADF of(R)-lmNCz,while no TADF is found in block-like single crystals(SC_(b)-form)with a larger △E_(st).The multiple ultralong phosphorescence(UOP)peaks in the spectrum are of complex origins,and they are related not only to ImNCz but also to a minor amount of impurities(ImNBd)in the crystal prepared in the laboratory.The dimer has similar phosphorescence emission wavelengths to the(R)-lmNCz-SC_(p) monomers.The complex composed of(R)-lmNCz and(R)-lmNBd contributes to the phosphorescent emission peak at about 600 nm,and the phosphorescent emission peak at about 650 nm is generated by(R)-lmNBd.This indicates that the impurity could also contribute to emission in molecular crystals.The present calculations clarify the relationship between the molecular aggregation and the light-emitting properties of the TADF emitters and will therefore be helpful for the design of potentially more useful TADF emitters.

Room-Temperature Phosphorescence and Lifetime of Fossil Resins (Amber) from Dominican Republic, Mexico, Baltic Sea, Myanmar, and Fushun, China

Amber can emit room temperature phosphorescence(RTP)under the well-known 365 nm fluorescence ultraviolet light.This paper is devoted to the phosphorescence study of 20 pieces of amber materials from the Dominican Republic,Mexico,Baltic sea,Myanmar,and Fushun,China.The results show that amber from the same geographic origin has similar shape in phosphorescence spectra.However,the shape of the amber phosphorescence spectra varies depending on their different localities.Burmite(amber from Myanmar)and Fushun amber have a bright yellow phosphorescence with a long lifetime,while the Dominican and Mexican ones are weaker and last shorter.The irradiation of Baltic amber becomes faint or even inert.Phosphorescence spectral Gaussian fitting results suggest an emission maximum near 550 nm in most amber samples.Their phosphorescence lifetime,analyzed through the exponential function fitting,is up to 1 second in Burmite and Fushun samples,shorter in the Dominican and Mexican ones,about 0.230 s,and the shortest in Baltic amber,close to 0.151 s.These variations of phosphorescence lifetime and intensity are related to the relative geological ages of these amber.It indicated that the phosphorescence agent was probably formed during the long geological time.While the anomaly occurred in Baltic amber,the only one found in a sea secondary deposit form,it demonstrated that the terrestrial geological environment these amber preserved has prevented the phosphorescence agent to be deactivated.

Study on Room-Temperature Phosphorescence of 1-Bromonaphthalene in Media of Surfactant and β-Cyclodextrin

Sdrictants(S) induced room-ternperature phorphorescence(RTP) frorn l-bromonaplithalene(l-BrN) in aerated aqueous solutions of o-cyclodextha(β-CD) hasbeco mvestigated m detail. lt has been fotmd that the partial incIu5ion and coil ofhydIocarbon chain of edctans at the mouth of the 6-CD ca\4ty' is reSPoedle foTbright RTP

Room-Temperature Organic Negative Differential Resistance Device Using CdSe Quantum Dots as the ITO Modification Layer

Room-temperature negative differential resistance （NDR） has been observed in different types of organic materials. However, detailed study on the influence of the organic material on NDR performance is still scarce. In this work, room-temperature NDR ＆ observed when CdSe quantum dot （QD） modified ITO is used as the electrode. Furthermore, material dependence of the NDR performance is observed by selecting materials with different charge transporting properties as the active layer, respectively. A peak-to-valley current ratio up to 9 is observed. It is demonstrated that the injection barrier between ITO and the organic active layer plays a decisive role for the device NDR performance. The influence of the aggregation state of CdSe QDs on the NDR performance is also studied, which indicates that the NDR is caused by the resonant tunneling process in the ITO/CdSe QD/organic active layer structure.

Detection of Oxygen Based on Host-Guest Doped Room-Temperature Phosphorescence Material

Quantitative oxygen detection,especially at low concentrations,holds significant importance in the realms of biology,complex environments,and chemical process engineering.Due to the high sensitivity and rapid response of the triplet excitons of phosphorescence to oxygen,pure organic room-temperature phosphorescence(RTP)materials have garnered widespread attention in recent years for oxygen detection.However,simultaneously achieving ultralong phosphorescence at room temperature and quantitative oxygen detection from pure organic host-guest doped materials poses challenges.The d ensely packed materials may decrease non-radiative decay to increase the phosphorescence,but are unsuitable for oxygen diffusion in oxygen detection.Herein,the oxygen sensitivity of host-guest doped RTP materials using 4-bromo-N,N-bis(4-(tertbutyl)phenyl)aniline(TPABuBr)as the host and 6-bromo-2-butyl-1H-benzo[de]isoquinoline-1,3(2H)-dione(NIBr)as the guest was developed.The doped material exhibits fluorescence-phosphorescence dual-emission behavior at room temperature.The tert-butyl groups in TPABuBr facilitate appropriate intermolecular spacing in the crystal state,enhancing oxygen permeability.Therefore,oxygen penetration can quench the phosphorescence emission.The observed linear relationship between the phosphorescence intensity of the doped material and the oxygen volume fraction conforms to the Stern-Volmer equation,suggesting its potential for quantitative analysis of oxygen concentration.The calculated limit of detection is 0.015%(φ),enabling the analysis of oxygen with a volume fraction of less than 2.5%(φ).Moreover,the doped materials demonstrate rapid response and excellent photostability,indicating their potential utility as oxygen sensors.This study elucidates the design and characteristics of NIBr/TPABuBr doped materials,highlighting their potential application in oxygen concentration detection and offering insights for the design of oxygen sensors.

Organic Host-Guest Materials with Bright Red Room-Temperature Phosphorescence for Persistent Bioimaging

Organic room-temperature phosphorescence(RTP)materials have attracted immense attention in bioimaging due to their long emission lifetime and large Stokes shift.RTP materials with long emission wavelength can improve the penetration depth for bioimaging.However,the design of red persistent RTP materials is still challenging.In this study,a fused-ring structure has been proposed to effectively decrease the triplet energy level,thus extending the emission wavelength of phosphorescence.In addition,the fused-ring structure exhibits a high molar extinction coefficient(ɛ)and high luminescence efficiency due to the rigid structure.A new class of crystalline hosts(iminodibenzyl,IDB)are developed to stabilize the triplet excitons that are generated from the fused-ring molecules.The maximum RTP wavelength of doping materials can reach 635 nm with a lifetime of 9.35 ms.Water-disperse nanoparticles are successfully prepared for in vivo time-resolved bioimaging,which eliminates the background fluorescence interference from biological tissues.These reveal a delicate design strategy for the construction of long-wavelength emissive RTP materials for high-resolution bioimaging.

Efficient transfer of metallophosphor excitons via confined polaritons in organic nanocrystals

We investigate the transfer of phosphorescent energy between co-assembled metallophosphors in crystalline nanostructures [Angew. Chem. Int. Ed. 57 7820(2018) and J. Am. Chem. Soc. 140 4269(2018)]. Neither Dexter's nor Forster's mechanism of resonance energy transfer(RET) could account fully for the observed rates, which exceed 85% with significant temperature dependence. But there exists an alternative pathway on RET mediated by intermediate states of resonantly confined exciton–polaritons. Such a mechanism was used to analyze artificial photosynthesis in organic fluorescents [Phys.Rev. Lett. 122 257402(2019)]. For metallophosphors, the confined modes act as extended states lying between the molecular S_(1) and T_(1) states, offering a bridge for the long-lived T_(1) excitons to migrate from donors to acceptors. Population dynamics with parameters taken entirely based on experiments fits the observed lifetimes of phosphorescence across a broad range of doping and temperature.

Enhancement of electroluminescent properties of organic optoelectronic integrated device by doping phosphorescent dye

Organic optoelectronic integrated devices（OIDs） with ultraviolet（UV） photodetectivity and different color emitting were constructed by using a thermally activated delayed fluorescence（TADF） material 4, 5-bis（carbazol-9-yl）-1, 2-dicyanobenzene（2 CzPN） as host. The OIDs doping with typical red phosphorescent dye [tris（1-phenylisoquinoline）iridium（Ⅲ）, Ir（piq）3], orange phosphorescent dye {bis[2-（4-tertbutylphenyl）benzothiazolato-N,C-（2＇）]iridium（acetylacetonate）,（tbt）2 Ir（acac）}, and blue phosphorescent dye [bis（2, 4-di-fluorophenylpyridinato）-tetrakis（1-pyrazolyl）borate iridium（Ⅲ）, FIr6] were investigated and compared. The（tbt）2 Ir（acac）-doped orange device showed better performance than those of red and blue devices, which was ascribed to more effective energy transfer. Meanwhile, at a low dopant concentration of 3 wt.%, the（tbt）2 Ir（acac）-doped OIDs showed the maximum luminance, current efficiency, power efficiency of 70786 cd/m^2, 39.55 cd/A, and 23.92 lm/W, respectively, and a decent detectivity of 1.07 × 10^11 Jones at a bias of -2 V under the UV-350 nm illumination. This work may arouse widespread interest in constructing high efficiency and luminance OIDs based on doping phosphorescent dye.

Highly Efficient Greenish-Yellow Phosphorescent Organic Light-Emitting Diodes Based on a Novel 2,3-Diphenylimidazo[1,2-a]Pyridine Iridium(Ⅲ) Complex

A cyclometalated greenish-yellow emitter 2,3-diphenylimidazo[1,2-a]pyridine iridium（Ill） complex is successfully synthesized and used to fabricate phosphorescent organic light-emitting diodes. The optimized device exhibits a greenish-yellow emission with the peak at 523nm and a strong shoulder at 557nm, corresponding to Commission Internationale de l＇Eclairage coordinates of （0.38, 0.68）. The full width at half maximum of the device is 93 nm, which is broader than the fac-tris（2-phenylpyridine）iridium [Ir（ppy）3] based reference device of 78 nm. Meanwhile, a maximum current efficiency of 62.6 cd/A （47.51m/W） is obtained. This result is higher than a maximum current efficiency of 54.8 cd/A （431m/W） of the Ir（ppy）a based device. The results indicate that this new iridium complex may have potential applications in fabricating high color rendering index white organic light emitting diodes.

Photoinduced Room-Temperature Phosphorescence of Triphenylamine-Phenothiazine Derivative-Doped Polymers

Photo-responsive room-temperature phosphorescent(RTP)materials have garnered significant interest due to the advantages of rapid response,spatiotemporal control,and contactless precision manipulation.However,the development of such materials remains in its infancy,underscoring the importance of exploiting novel and efficient light-responsive RTP molecules.In this work,three phenothiazine derivatives of TPA-PTZ,TPA-2PTZ,and TPA-3PTZ were successfully synthesized via the Buchwald-Hartwig C—N coupling reaction.By embedding these molecules as RTP guests into polymethyl methacrylate(PMMA)matrix,photo-induced RTP properties were realized.Upon sustained UV irradiation,there was an enhancement of 19 times in the quantum yield to reach a value of 5.68%.Remarkably,these materials exhibit superior alongside robust light and thermal stability,maintaining high phosphorescence intensity even after prolonged UV exposure(irradiation for>200 s by a 365 nm UV lamp with the power of 500μW·cm-2)or at higher temperature up to 75℃.The outstanding properties of these photo-induced RTP materials make them promising candidates for applications in information encryption,anti-counterfeiting,and advanced optical materials.

Matrix-Mediated Color-Tunable Ultralong Organic Room Temperature Phosphorescence of 7H-Benzo[c]carbazole Derivatives

Building on the recent systematic research on 1Hbenzo[f]indole(Bd),an important advancement in constructing ultralong organic room temperature(UORTP)materials with a universal strategy via a readily obtained unit(7H-Benzo[c]carbazole,BCz)is proposed in this work.Pure powders of BCz and its derivatives merely exhibit blue fluorescence at ambient condition.However,when BCz and its derivatives are dispersed into polymer or powder matrixes,strong photo-activated green UORTP can be observed from their doped systems at room temperature.Moreover,the UORTP color can be tuned between green and yellow depending on the matrix.The ultralong phosphorescence originates from the generation of charge-separated states via radicals.The matrixes play a key role in both stabilizing charge-separated states and controlling UORTP color.More interestingly,when using polymethyl methacrylate as matrix,the doped films achieve stronger photo-activated ultralong phosphorescence underwater than in air at room temperature.Comparedwith Bd,BCz achieves better performance not only in ultralong phosphorescence properties but also in practical applications.This work gains a deeper insight into the mechanism of UORTP and paves a new approach to applying organic phosphorescent materials to underwater coating and imaging.

Platinum complexes as phosphorescent emitters in highly efficient organic light-emitting diodes

Applications of platinum complexes as phosphorescent emitters in high efficiency organic light-emitting diodes （OLEDs） were shortly discussed in this paper. Key recent studies on highly efficient blue, green, red and white-phosphorescent OLEDs based on Pt complexes are presented in terms of efficiency and color quality.

Spectral Characteristics of White Organic Light-emitting Diodes Based on Novel Phosphorescent Sensitizer

White organic light-emitting diodes were fabricated by using a novel phosphorescence bis（1,2-diphenyl-1H-benzoimidazole）iridium（acetylacetonate）[（pbi）2Ir（acac）] as sensitizer and a fluorescent dye of 4- （dicyanomethylene）-2-t-butyl-6-（1,1,7,7-tetramethyljulolidyl-9-enyl）-4H-pyran （DCJTB） codoped into a carbazole polymer of poly（N-vinylcarbazole） （PVK）. Through characterizing the UV-Vis absorption spectra, the photoluminescence spectra of （pbi）2Ir（acac） and DCJTB, and the electroluminescence spectral properties of the WOLEDs, the energy transfer mechanisms of the codoped polymer system were deduced. The results demonstrate that the luminescent spectra with different intensity of （pbi）2Ir（acac） and DCJTB were co-existent in the EL spectra of the blended system, which is ascribed to an incomplete energy transfer process in the EL process. The efficient Forster and Dexter energy transfer between the host and the guests enabled a strong yellow emission from （pbi）2Ir（acac） and DCJTB, where （pbi）2Ir（acac） plays an important role as a phosphorescent sensitizer for DCJTB. With the blue emitting-layer of N,N＇-diphenyl-N,N＇-bis（1- naphthyl）（1,1＇-biphenyl）-4,4＇-diamine, the codoped system device achieved white emission. The codoped system showed that its Commissions Internationale de 1＇Eclairage coordinates were more independent of the variation of bias voltage than those of phosphorescent doped PVK systems.

High-Efficiency Green Phosphorescent Organic Light-Emitting Diode Based on Simplified Device Structures

A high-efficiency green phosphorescent organic light emitting diode with a simplified structure is achieved that is free of a hole transport layer. The design of this kind of device structure not only saves the consumption of organic materials but also greatly reduces the structural heterogeneities and effectively facilitates the charge injection into the emissive layer. The resulting green phosphorescent organic light-emitting diodes （PHOLEDs） exhibit higher electroluminescent efficiency. The maximum external quantum efficiency and current efficiency reach 23.7% and 88 cd/A, respectively. Moreover the device demonstrates satisfactory stability, keeping 23.7% and 88cd/A, 22% and 82cd/A, respectively, at a luminance of 100 and 1000cd/m2. The working mechanism for achieving high efficiency based on such a simple device structure is discussed correspondingly. The improved charge carrier injection and transport balance are proved to prominently contribute to achieve the high efficiency and great stability at high luminance in the green PHOLEDs.

A Mixed Host Emitting Interlayer Based on CBP:TPBi in Green Phosphorescent Organic Light-Emitting Diodes

A series of green phosphorescent organic light-emitting diodes based on bipolar-transporting material 4,4Lbis- （carbazol-9-yl） biphenyl （CBP） are prepared. We insert a mixed host emitting interlayer （CBPx： electron- transporting material 1,3,＆tris （N-phenylbenzimidazole-2yl） （TPBi）1-X） in the middle of the emitting layer, and the best performance appears when x is 2/3. The position of this interlayer can also affect the performanee of phosphorescent organic light-emitting diodes. When this interlayer is close to the side of the electron transporting layer, the maximum value of luminance, the current efficiency and the power efficiency are 34090cd/m2 at 12 V, 60. 6 cd/A and 56.6 lm/W, respectively.