Afterglow bio-applications by utilizing triplet excited states of organic materials

Organic room temperature phosphorescence(RTP) materials with persistent afterglow exhibit good biocompatibility, high signal to noise ratio and time resolved imaging characteristics in bio-applications. Moreover, they can serve as hypoxia detection probes and photodynamic therapy agents for the sensitivity of triplet excitons toward oxygen in the surroundings. In this review, the recent progress of in vitro and in vivo afterglow bioimaging is presented by utilizing organic RTP materials. The strategies of molecular design and controlling methods of molecular packing were summarized, to prompt this new rising research field, with the emphasis on high intensity, ultralong lifetimes and red-shifted wavelengths of phosphorescence emission.

Transient Spectroscopic Properties of [60]Fullerene-Containing Cyclic Sulphoxide

The properties of the triplet excited state of [60]fullerene-containing cyclic sulphoxide have been investigated by time-resolved absorption spectroscopy. Transient absorption bands of [60]fullerene-containing cyclic sulphoxide showed two decay-components, which were attributed to triplet excited states of different spin multiplicity. The properties of photoexcited states of [60]fullerene-containing cyclic sulphoxide are also reported.

Broadband Visible Light Harvesting BODIPY-Perylene Dyad and Triad:Synthesis,Photophysical Properties,and Photooxidation Applications

In this study,diodo boron dipyrromethene(BODIPY)is employed a8 the energy donor and 3,4,9,10-perylene tetracarboxylic dianhydride(PDA)as the energy acceptor,enabling the synthesis of two new compounds:a BODIPY-perylene dyad named P1,and a triad named P2.To investigate the impact of the energy donor on the photophysical processes of the system,P1 comprises one diodo-BODIPY unit and one PDA unit,whereas P2 contains two diodo-BODIPY moieties and one PDA unit.Due to the good spectral complementarity between diiodo-BODIPY and PDA,these two compounds exhibit excellent light-harvesting capabilities in the 400-620 nm range.Steady-state fluorescence spectra demonstrate that when preferentially exciting the diodo-BODIPY moiety,it can effectively transfer energy to PDA;when selectively exciting the PDA moiety,quenching of PDA fluorescence is observed in both P1 and P2.Nanosecond transient absorption results show that both compounds can efficiently generate triplet excited states,which are located on the PDA part.The lifetimes of the triplet states for these two compounds are 103 and 89μs,respectively,significantly longer than that of diiodo-BODIPY.The results from the photooxidation experiments reveal that both P1 and P2 demonstrate good photostability and photooxidation capabilities,with P2 showing superior photooxidative efficiency.The photooxidation rate constant for P2 is 1.3 times that of P1,and its singlet oxygen quantum yield is 1.6 times that of P1.The results obtained here offer valuable insights for designing new photosensitizers.

Singlet relaxation dynamics and long triplet lifetimes of thiophene-coupled perylene diimides dyads:New insights for high efficiency organic solar cells

In the active layer of organic solar cells(OSCs),the lifetime of triplet excitons is one of the decisive factors in the diffusion length and therefore has important impact on the power conversion efficiency of the devices.Herein,we have investigated singlet excited state relaxation dynamics and their triplet exciton lifetimes of two thiophene-coupled perylene diimides(PDI)dyads(2 PDI-Th and fused-2 PDI-Th),in order to provide a unique explanation in depth on their different performances in OSC devices.From the transient absorption(TA)spectra,the singlet excitons of 2 PDI-Th form excimers in the time scale of 1.5 ps.Then the excimers go into the triplet state via intersystem crossing(ISC).In fused-2 PDI-Th,triplet excitons are generated directly from the singlet excited excitons via the efficient ISC.Density functional theory(DFT)calculations further support the formation of excimers.DFT results indicate that 2 PDI-Th exhibits an H-typed molecular configuration which is beneficial to form the excimers,while fused-2 PDITh gives a twisted X-shaped configuration in the optimized ground and excited state.In steady-state emission spectra,2 PDI-Th shows abroad and featureless spectral characteristics of the excimers with a decay time of 840 ps,which is much shorter than those of PDI(5.5 ns)and fused-2 PDI-Th(3.3 ns).The triplet lifetime(67 ms)of fused-2 PDI-Th is factor of 3 longer than that of 2 PDI-Th(22 ms).These results demonstrate that ring-fused structure is an efficient strategy to eliminate excimer formation and prolong the lifetime of triplet excitons,which provides a new insight for design of optoelectronic molecules for high efficiency organic solar cells.

Twisted Phosphors that Violate Kasha's Exciton Model in Organic Systems

Kasha's exciton model proposes that T1 energy levels of organic compounds are insensitive to molecular aggregation and microenvironment change because of negligible small transition dipole moments of T1 states.This model holds true in most organic systems till now.Here we report the fabrication of twisted organic phosphors with intramolecular charge transfer characters and flexible molecular structures.When doped into different organic matrices,the twisted phosphor adopts different conformation,exhibits distinct phosphorescence colors and T1 energy levels,which violates Kasha's exciton model in organic system.Given that the change of phosphorescence colors and maxima can be readily distinguished by human eyes and conventional instrument,the twisted phosphors would be exploited as a new type of molecular probe,which would exhibit potential application in optical sensing and stimuli-responsive systems.

Photophysical and photochemical processes of riboflavin (vitamin B_2) by means of the transient absorption spectra in aqueous solution

Using time-resolved techniques of 337 and 248 nm laser flash photolysis, the photo physical and photochemical processes of riboflavin (RF, vitamin B2) were studied in detail in aqueous solution. The excited triplet state of riboflavin (3RF*) was produced with 337 nm laser, while under 248 nm irradiation, both3RF* and hydrated electron (eaq) formed from photoionization could be detected. Photobiological implications have been inferred on the basis of reactivity of3RF* including energy transfer, electron transfer and hydrogen abstraction. The RF·+ was generated by oxidation of SO4 ·-radical with the aim of confirming the results of photolysis.

Cyclic(Amino)(Aryl)Nitrenium Cations with Lewis Acidity Controlled by Remote Substituents

N-Heterocyclic nitrogen Lewis acids are important in synthetic chemistry.Stable cyclic(amino)(aryl)nitrenium cations,cyc-1^(+)-cyc-3^(+),were synthesized by chemical oxidation of aryl azo compounds with different substituents,H and I,at the para positions of the phenyl group.The excited triplet states of cyc-1^(+)-cyc-3^(+) abstract H-atoms step by step to generate radical intermediates cyc-1H^(*+-)cyc-3H^(*+)traced by EPR spectroscopy and products cyc-1H^(2+)-cyc-3H^(2+) characterized by single crystal X-ray diffraction.The Lewis acidity of species cyc-1^(+)-cyc-3^(+) are remote substituent-dependent.Cyc-2^(+)-cyc-3^(+) have much higher acidity than those previously reported congeners based on energies of LUMOs.The electrophilicity enables them to form Lewis adducts with neutral Lewis base Me_(3)P,and to gain one-electron to produce neutral radicals cyc-1^(*)-cyc-3^(*).

One-dimensional alkylate-bridged Würster's blue-based diradical dications

By using weakly coordinating anions we succeeded in the stabilization and isolation of two Wfirster＇s blue-based diradicaloid dications with saturated spacers. Their geometries and electronic structures were investigated by various experiments in conjunction with DFT calculations. Both one-dimensional alkylate-bridged dications show considerable diradical character with spacer-dependent singlet-triplet energy gaps. One of them displays a much enhanced diradical character and could basically be viewed as a pure diradical with degeneracy of singlet and triplet states.

Nearly 100% exciton utilization in highly efficient red OLEDs based on dibenzothioxanthone acceptor

Improving the utilization of excitons has always been an important topic for the development of electroluminescence devices.In this work,we designed and synthesized three red TADF emitters TPA-DBT12,TPA-DBT3 and DTPA-DBT by employing dibenzothioxanthone(DBT)acceptor framework to stabilize the locally excited triplet state to participate in the reverse intersystem crossing(RISC)process.The fast RISC process and singlet radiation decay process gave rise to evidently enhanced exciton utilization.All of the red OLEDs based on these materials showed maximum EQE over 11% and high exciton utilization close to 100%.This work not only extend the acceptor framework for red materials but also provide a new perspective for the design of highly efficient red TADF materials with 100% exciton utilization by managing locally excited triplet state.

Advanced charge transfer technology for highly efficient and long-lived TADF-type organic afterglow with near-infrared light-excitable property

Heavy atom effects and n-π*transitions have been frequently reported to enhance room-temperature organic phosphorescence efficiency but lead to shortage of phosphorescence lifetimes.Unlike these reported studies,we conceive the incorporation of advanced charge transfer(CT)technology to boost room-temperature organic afterglow efficiency and simultaneously maintain afterglow lifetimes.Here we design difluoroboronβ-diketonate(BF2bdk)CT compounds with moderate singlet-triplet splitting energy(ΔEST)of around 0.4 e V,and relatively large spin-orbit coupling matrix elements(SOCME(S_(1)-T_(1)),1–10 cm^(-1))to achieve efficient intersystem crossing(ISC)and moderate rates of reverse intersystem crossing(kRISC,1–10 s^(-1)).The advanced CT technology,which includes multiple electron-donating groups and orthogonal donor-acceptor arrangement,have been found to narrowΔESTand enhance both ISC and RISC.Meanwhile,the organic matrices suppress nonradiative decay of BF2bdk’s T1states by their rigid microenvironment.Consequently,thermally activated delayed fluorescence(TADF)-type organic afterglow materials can be achieved with afterglow efficiency up to 83.0%,long lifetimes of 433 ms,excellent processablility,as well as advanced anti-counterfeiting and information encryption.Furthermore,with the aid of up-conversion materials and through radiative energy transfer,TADF-type afterglow materials with aqueous dispersity and near-infrared light-excitable property have been achieved,which paves the way for biomedical applications.