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 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.

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.

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.

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.

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.

Preparation of Phosphors MAl_2O_4∶Eu^(2+)(M=Ca,Sr,Ba) by Microwave Heating Technique and Their Phosphorescence

The phosphors of the alkaline earth aluminates coactivated with europium and other rare earths were successfully obtained by microwave radiation heating technique.These phosphors have bright phosphorescence and maintain their afterglow for a fairly long duration.

Sol-gel preparation and phosphorescence property of Mn^(2+)-doped zinc boro-silicate glass thin films

Mn2＋-doped zinc borosilicate （ZBSM） glass thin films were first synthesized by sol-gel method. In the experiment, a thin gel film was depos-ited onto quartz glass substrates by dip-coating method and then heat-treated to form a Mn2＋-doped zinc borosilicate glass thin film. Long lasting phosphorescence （LLP） and photo-stimulated long lasting phosphorescence （PSLLP） were found in the film sample. According to fluorescence spectra, LLP emission spectra, and PSLLP emission spectra, both LLP and PSLLP emissions are attributed to the energy level transition of 4Eg→4A1g from Mn2＋. Both the phosphorescence intensity decay curves contain a fast decay component and another slow decay one. The thermoluminescence （TL） spectra show that the sample has two kinds of traps at least and their energy level values are about 0.8 eV and 1.02 eV, which could be estimated by the Randall and Willcins formula. The infrared absorption spectra （IR） consist of characteristic vi-bration bands of Si-O-Si, Si-O-Zn, B-O in [BO3], B-O group, and Zn-O in [ZnO4]. Moreover, image storage and logical operation of the ZBSM film were carried out successfully through an experiment analogues of optical storage.

Preparation of the Phosphors BaAl_2O_4:Eu, RE (RE=Dy, Ho) by Microwave Heating Technique and Observation of Long Phosphorescence

The phosphors BaAl2O4: Eu2+. RE (RE=Dy. Ho) have been prepared by the microwave heating technique. The long-lasting phosphorescence in the phosphors of the barium aluminate activated with europium and other rare earths has been observed for the first time.

Study on the Interaction of Mitomycin C with ct-DNA by Pd-Porphin Room Temperature Phosphorescence Probe

Anticancer drug Mitomycin C (MMC) quenches remarkably phosphorescence and reduces lifetime of phosphorescence probe, Pd-meso-tetrakis-(4-trimethylaminophenyl)porphin (Pd-TAPP), in the presence of calf thymus DNA. These results may be attributed to the site competition of MMC with the probe and electron transfer between MMC and probe. MMC also increases polarization degree of the probe by covalent drug-DNA or DNA-drug-DNA crosslinking.

Long Lasting Phosphorescence in Eu^(2+) and Ce^(3+) Co-Doped Strontium Borate Glasses

Long lasting phosphorescence (LLP) was observed in Eu2+, Ce3+ co-doped strontium borate glasses prepared under the reducing atmosphere due to the emission of both Eu2 + and Ce3+ . The methods of photoluminescence, thermolu-minescence and phosphorescence were used to study the samples, and possible mechanism was suggested. The co-doping of Ce3 + ions poisoned the phosphorescence emission of Eu2 + because of the competition to obtain the trapped electron . The phosphorescence of Ce3 + in the sample decays more quickly than that of Eu2 + , which is suggested for the reason that the emission energy of Ce3 + is higher or the distance between Ce3 + and electron traps of the glasses is longer.

A pilot study of the dynamics of tissue oxygenation in vivo using time-resolved phosphorescence imaging

Oxygenation of tissues plays an important role in the development and progression of tumor to treatment effects.Method of metalloporphyrines phosphorescence quenching by oxygen is one of the ways to measure dynamics of the oxygen concentration in the tissues by phosphorescence lifetime imaging of meso-tetra(sulfophenyl)tetrabenzoporphyrin Pd(Ⅱ)(TBP)using the time-correlated single photon counting(TCSPC)method.It has been shown that phosphorescence lifetime of the sensor in S37 tumor in vivo varied in the range of 130 to 290μs after both topical and intravenous administration of TBP.It indicates that oxygen level in tumors was lower compared to normal tissues where TBP phosphorescence has not been detected.Phosphorescence lifetimes of TBP increased in the solid tumor and in the muscle after photodynamic therapy of solid tumor that demonstrates oxygen consumption during treatment and possibly stopping the blood flow and hence the oxygen supply to the tissues.

BRIGHT LONG AFTERGLOW PHOSPHORESCENCE GLASS MADE OF SrAl_(2)O_(4): Eu^(2+), Dy^(3+) AND GLASS FRITS

Bright long afterglow phosphorescence glasses were prepared by using SrAl2O4： Eu^2＋, Dy^3＋ phosphors and suitable glass frits together. The SrAl2O4： Eu^2＋, Dy^3＋ phosphors were initially prepared by the solid reaction method. Three kinds of glass frits were prepared to match the SrAl2O4： Eu^2＋, Dy^3＋ phosphors. Effects of the compositions of the glass frits, the ratios of the phosphors to the frits us well us the firing temperature and firing times on the properties of the samples were discussed. XRD analysis indicated the samples exhibited the typical diffraction peaks of SrAlwO4： Eu^2＋, Dy^3＋. The emission spectra of the samples showed broad bands peaking at 510nm.The excitation spectra of the samples showed broad bands ranging from 300 to 480hm. These are believed due to the 5d4f-4f transitions of Eu^2＋ in the SrAl2O4： Eu^2＋, Dy^3＋ phosphors. The afterglow luminescence of the samples excited by a 40W fluorescence lamp for 30min can be observed in the dark for more lOh with the naked eyes. It can find wide applications in many fields.

Determination of trace arsenic(V) by catalytic solid substrate-room temperature phosphorescence quenching method

In the H2SO4 medium and in the presence of dodecylbenzene sulfonic acid sodiumsalt (DBS), dimethyl yellow (R) could emit strong and stable solid substrate room temperature phosphorescence (RTP) on filter paper. And NaIO4 could oxidize R to cause the RTP quenching. Arsenic(V) could catalyze the reaction of NaIO4 oxidizing R, which caused the RTP sharply quenching. The reducing value of phosphorescence intensity (ΔIp) for the system with DBS is 3.3 times higher than that without DBS. Moreover, the ΔIp is proportional to the concentration of As(V). Based on the facts above, a new RTP quenching method for the determination of trace As(V) has been established.

Probing defects in ZnO by persistent phosphorescence

Native point defects in ZnO are so complicated that most of them are still debating issues, although they have been studied for decades. In this paper, we experimentally reveal two sub-components usually hidden in the low energy tail of the main broad green luminescence band peaking at 547 nm （-2.267 eV） in intentionally undoped ZnO single crystal by selecting the below-band-gap （BBG） optical excitations （e.g. light wavelengths of 385 nm and 450 nm）. Moreover, both sub-components are manifested as long persistent phosphorescence once the BBG excitations are removed. With the aid of a newly developed model, the energy depths of two electron traps involved within the long lived orange luminescence are determined to be 44 meV and 300 meV, respectively. The candidates of these two electron traps are argued to be most likely hydrogen and zinc interstitials in ZnO.

Preparation of Long-Lasting Phosphorescence (LLP) Glass-Ceramic Materials

Three kinds of glass-ceramics, i.e., Mn 2+ doped zinc borosilicate, Eu 2+, Dy 3+ co-doped strontium aluminoborate and Eu 2+, Nd 3+ co-doped calcium aluminoborate were prepared, whose phosphorescence emission band peaks at 525, 516 and 464 nm, respectively. In preparation of these glass-ceramics the base glasses were gained by heating the mixed starting materials at high temperature to get the transparent glasses; then those glasses were heat-treated and turned to opaque glass-ceramics. X-ray diffraction (XRD) shows that the crystallites are ZnSiO 4, SrAl 2O 4 and α-CaAl 2B 2O 7, respectively. It is a useful way to get new LLP materials by the method reported in this work that may be considered as “from glass to crystal”.

Metal nanoparticle-enhanced room temperature phosphorescence of diiodofluorescein on the filter paper substrate

Metal-enhanced room temperature phosphorescence of diiodofluorescein was first observed on filter paper surface.The phosphorescence intensity is 2.5-fold brighter from diiodofluorescein on silver nanoparticles-deposited filter paper as compared with an identical control sample without silver nanoparticles.Furthermore,enhanced absorption was also observed for the same system.Our findings suggest that both singlet and triplet states can couple to surface plasmons and enhance phosphorescence quantum yields at ...

Long Lasting Phosphorescence and Photo-Stimulated Long Lasting Phosphorescence in Tb^(3+)-doped Strontium Borosilicate Glasses

Long lasting phosphorescence （LLP） and photo-stimulated long lasting phosphorescence （PSLLP） were observed in Tb^3＋-doped strontium borosilicate glasses. The green phosphorescence arises fromf-f transitions of Tb^3＋ and can be observed with naked eyes in the dark for up to 10 hours after the irradiation with a UV lamp （λmax =254 nm） for 30 min at room temperature. The glass could re-emit LLP under the stimulation of a UV lamp （λmax=366 rim） for 60 seconds after the LLP disappeared. The re-emitted LLP is called PSLLP. The glass sample was characterized by the fluorescence and thermoluminescence spectra, respectively. The possible mechanism of the LLP and PSLLP was also discussed.

Red Long Lasting Phosphorescence of Mn^(2+) Doped Zinc Phosphate Glasses

Mn^2＋ doped ZnO-P2O5 glasses emit red fluorescence, which shows that Mn^2＋ ion doped in zinc phosphate glass is octahedrally coordinated. Moreover, glass samples exhibit bright red long lasting phosphorescence （LLP） when the mole percent of ZnO are more than 60%. After turnoff the irradiation source of UV lamp peaking at 254 nm, the red phosphorescence can be observed for about 6 h in the limit of light perception for naked eyes （0.32 mcd/m^2）. Photoluminescence （PL） spectra, LLP emission spectra and decay curves were detected. Increasing MnO or ZnO content, the phosphorescence intensity can be improved distinctly and the emission wavelength can be also adjusted from 595 nm to 628 nm. According to the structural characteristic of zinc phosphates glasses, we suggest that non-bridge oxygen （NBO） is probably related with the arising of LLE Meantime, the variation of crystal field intensity induced that the LLP emission wavelength red shifts.