Radiative Rate Research Articles

Luminescent carbene-copper(i)-amide polymers for efficient host-free solution-processed OLEDs.

Luminescent metallopolymers have attracted broad interest in the fields of healthcare and organic electronics. However, polymeric emitters based on earth-abundant metal complexes are scarce. Here, two series of Cu(i) polymers, PMAC-x and PCAAC-x (x = 1-3) have been developed using two kinds of Cu(i)-based carbene-metal-amide (CMA) complexes as side-chain emitter units to combine with a nonconjugated polystyrene backbone. These Cu(i) polymers emit via distinct thermally activated delayed fluorescence or dominant phosphorescence, inherited from the grafted Cu(i)-based CMA units. Particularly, the PMAC-x polymers exhibit high photoluminescence quantum efficiencies of up to 0.78, short emission lifetimes of down to 0.66 μs, and fast radiative rates of up to 106 s-1 in neat films. Thanks to the good encapsulation effect of the polystyrene backbone, these Cu(i) polymers not only demonstrate favorable moisture stability but also show significant aggregation-induced emission. The resultant host-free solution-processed organic light-emitting diodes (OLEDs) achieve outstanding electroluminescence performance with a record external quantum efficiency of 13.8% at a practical luminance of ∼100 nits, representing state-of-the-art device efficiency for metallopolymer-based OLEDs. This work not only presents the first example of CMA polymers but also provides the future direction of polymeric emitters from earth-abundant metal complexes for the OLED application.

One Dianionic Luminophore with Three Coordination Modes Binding Four Different Metals: Toward Unexpectedly Phosphorescent Transition Metal Complexes.

This work reports on a battery of coordination compounds featuring a versatile dianionic luminophore adopting three different coordination modes (mono, bi, and tridentate) while chelating Pd(II), Pt(II), Au(III), and Hg(II) centers. An in-depth structural characterization of the ligand precursor (H2 L) and six transition metal complexes ([HLPdCNtBu], [LPtCl], [LPtCNtBu], [LPtCNPhen], [HLHgCl], and [LAuCl]) is presented. The influence of the cations and coordination modes of the luminophore and co-ligands on the photophysical properties (including photoluminescence quantum yields (ΦL ), excited state lifetimes (τ), and average (non-)radiative rate constants) are evaluated at various temperatures in different phases. Five complexes show interesting photophysical properties at room temperature (RT) in solution. Embedment in frozen glassy matrices at 77K significantly boosts their luminescence by suppressing radiationless deactivation paths. Thus, the Pt(II)-based compounds provide the highest efficiencies, with slight variations upon exchange of the ancillary ligand. In the case of [HLPdCNtBu], both ΦL and τ increase over 30-fold as compared to RT. Furthermore, the Hg(II) complex achieves, for the first time in its class, a ΦL exceeding 60% and millisecond-range lifetimes. This demonstrates that a judicious ligand design can pave the way toward versatile coordination compounds with tunable excited state properties.

Large Fluorescence Enhancement via Lossless All-Dielectric Spherical Mesocavities.

Nano- and microparticles are popular media to enhance optical signals, including fluorescence from a dye proximal to the particle. Here we show that homogeneous, lossless, all-dielectric spheres with diameters in the mesoscale range, between nano- (≲100 nm) and micro- (≳1 μm) scales, can offer surprisingly large fluorescence enhancements, up to F ∼ 104. With the absence of nonradiative Ohmic losses inherent to plasmonic particles, we show that F can increase, decrease or even stay the same with increasing intrinsic quantum yield q0, for suppressed, enhanced or intact radiative decay rates of a fluorophore, respectively. Further, the fluorophore may be located inside or outside the particle, providing additional flexibility and opportunities to design fit for purpose particles. The presented analysis with simple dielectric spheres should spur further interest in this less-explored scale of particles and experimental investigations to realize their potential for applications in imaging, molecular sensing, light coupling, and quantum information processing.

Plasmonic Nanocone Scanning Antenna: Fabrication and Optical Properties

Optical antennas are nanostructures that introduce unprecedented possibilities for light–matter interaction at the nanoscale. An appropriately tailored plasmonic antenna can enhance the total radiative decay rate and modify the angular radiation pattern of a single‐quantum emitter through controlled near‐field coupling. Despite their ability to surpass the fundamental diffraction limit and confine the electromagnetic field to a tiny mode volume, fabricating 3D sharp scanning nanoscale plasmonic structures with desired aspect ratio is yet an ambitious goal. The fabrication of nanocones by gold evaporation on commercial atomic force microscopy probes followed by a focused ion beam milling technique is presented. The method is versatile and allows the fabrication of nanocones with desired dimensions around 100 nm along with an aspect ratio of ≈1. Their optical properties are studied and it is shown how the variation in the refractive index of the dielectric substrate affects the localized surface plasmon resonance of the nanocones, the decay rate enhancement, and the quantum yield of an emitter relevant for fluorescence/Raman scanning experiments. Theoretical studies using finite‐difference time‐domain calculations have guided the fabrication process and are consistent with experimental results.

Tridentate C^N^N ligands as cyclometalated luminophores for phosphorescent Pt(II) complexes – A case study concerning the influence of the substitution pattern and the co-ligands on the excited state properties

In this work, the synthesis as well as the structural and photophysical characterization encompassing a series of Pt(II) complexes bearing cyclometalating pyrazole-based C^N^N ligands as tridentate luminophores are reported. By varying the substitution pattern of the main luminophore and by exchanging the ancillary co-ligand, different Pt(II) complexes were synthesized and compared regarding their excited state properties. The complexes C1-C8 bear differently decorated luminophores and a chlorido co-ligand; compounds C9–15 possess stronger ancillary ligands, such as cyanido and substituted acetylido derivates. While all complexes showed luminescence from metal-perturbed ligand-centered triplet states (3MP-LC), there are significant differences regarding the photoluminescence lifetimes (τ) and quantum yields (ΦL), both resulting from variations in the average radiative (kr) and radiationless (knr) deactivation rate constants. Although the chlorido complexes generally show lower ΦL, the OH-substituted compound C3 reaches a surprisingly high value of 36 %. Complex C9 with a cyanido co-ligand shows the longest τ of the series with 15.76 µs at room temperature in an Ar-purged solution, whereas all chlorido complexes C1-C8 possess lifetimes below 1.90 µs. The highest ΦL is achieved with phenylacetylido as the co-ligand. In general, the insertion of electron-withdrawing moieties at the main luminophore on the meta-position (with respect to the cyclometallation site) has a detrimental impact on the overall performance, whereas electron donors improve the photoluminescence efficiency. The t-butyl group on the main luminophore enhances the processability without affecting the excited state properties.

Photocatalytic Reduction of CO2 to HCOOH and CO by a Phosphine‐Bipyridine‐Phosphine Ir(III) Catalyst: Photophysics, Nonadiabatic Effects, Mechanism, and Selectivity

AbstractPhotocatalytic CO2 reduction is one of the best solutions to solve the global energy crisis and to realize carbon neutralization. The tetradentate phosphine‐bipyridine (bpy)‐phosphine (PNNP)‐type Ir(III) photocatalyst, Mes‐IrPCY2, was reported with a high HCOOH selectivity but the photocatalytic mechanism remains elusive. Herein, we employ electronic structure methods in combination with radiative, nonradiative, and electron transfer rate calculations, to explore the entire photocatalytic cycle to either HCOOH or CO, based on which a new mechanistic scenario is proposed. The catalytic reduction reaction starts from the generation of the precursor metal‐to‐ligand charge transfer (3MLCT) state. Subsequently, the divergence happens from the 3MLCT state, the single electron transfer (SET) and deprotonation process lead to the formation of one‐electron‐reduced species and Ir(I) species, which initiate the reduction reaction to HCOOH and CO, respectively. Interestingly, the efficient occurrence of proton or electron transfer reduces barriers of critical steps. In addition, nonadiabatic transitions play a nonnegligible role in the cycle. We suggest a lower free‐energy barrier in the reaction‐limiting step and the very efficient SET in 3MLCT are cooperatively responsible for a high HCOOH selectivity. The gained mechanistic insights could help chemists to understand, regulate, and design photocatalytic CO2 reduction reaction of similar function‐integrated molecular photocatalyst.

Photocatalytic Reduction of CO2 to HCOOH and CO by a Phosphine-Bipyridine-Phosphine Ir(III) Catalyst: Photophysics, Nonadiabatic Effects, Mechanism, and Selectivity.

Photocatalytic CO2 reduction is one of the best solutions to solve the global energy crisis and to realize carbon neutralization. The tetradentate phosphine-bipyridine (bpy)-phosphine (PNNP)-type Ir(III) photocatalyst, Mes-IrPCY2, was reported with a high HCOOH selectivity but the photocatalytic mechanism remains elusive. Herein, we employ electronic structure methods in combination with radiative, nonradiative, and electron transfer rate calculations, to explore the entire photocatalytic cycle to either HCOOH or CO, based on which a new mechanistic scenario is proposed. The catalytic reduction reaction starts from the generation of the precursor metal-to-ligand charge transfer (3 MLCT) state. Subsequently, the divergence happens from the 3 MLCT state, the single electron transfer (SET) and deprotonation process lead to the formation of one-electron-reduced species and Ir(I) species, which initiate the reduction reaction to HCOOH and CO, respectively. Interestingly, the efficient occurrence of proton or electron transfer reduces barriers of critical steps. In addition, nonadiabatic transitions play a nonnegligible role in the cycle. We suggest a lower free-energy barrier in the reaction-limiting step and the very efficient SET in 3 MLCT are cooperatively responsible for a high HCOOH selectivity. The gained mechanistic insights could help chemists to understand, regulate, and design photocatalytic CO2 reduction reaction of similar function-integrated molecular photocatalyst.

Optimizing performance and energy consumption in GaN(n)/InxGa1-xN/GaN/AlGaN/GaN(p) light-emitting diodes by quantum-well number and mole fraction

High performance and safe light-emitting devices (LEDs) are needed. Highly efficient IIIV nitride semiconductors are known for short-wavelength LEDs. Multiple-quantum well (MQW) are considered in LEDs. Influence of MQW and indium concentration on LED performance are studied here in GaN(n)/InxGa1-xN(i)/GaN(i)/AlGaN(p)/GaN(p) LEDs, where GaN(n) and GaN(p) have different dopants to formulate junctions, InxGa1-xN(i) is a 3 nm-thick intrinsic QW, GaN(i) is barrier intrinsic layer and AlGaN(p) is a 15 nm-thick electron blocking layer (EBL). Simulation is performed by Tcad-Silvaco. Current versus voltage (I-V) plots, luminosity power, band diagram, spectrum response, radiative recombination rate and electric field effect, are investigated to rationalize effects of InxGa1- xN(i) QW number and x. Increasing (x) improves radiative recombination rate, spectral power and band gap at less current. Devices with 6 quantum wells and x= 0.16 or 0.18 exhibit best performance. Minimizing x at 0.16, at high performance, is described.

Stable blue phosphorescent organic LEDs that use polariton-enhanced Purcell effects.

Phosphorescent organic light-emitting diodes (PHOLEDs) feature high efficiency1,2, brightness and colour tunability suitable for both display and lighting applications3. However, overcoming the short operational lifetime of blue PHOLEDs remains one of the most challenging high-value problems in the field of organic electronics. Their short lifetimes originate from the annihilation of high-energy, long-lived blue triplets that leads to molecular dissociation4-7. The Purcell effect, the enhancement of the radiative decay rate in a microcavity, can reduce the triplet density and, hence, the probability of destructive high-energy triplet-polaron annihilation (TPA)5,6 and triplet-triplet annihilation (TTA) events4,5,7,8. Here we introduce the polariton-enhanced Purcell effect in blue PHOLEDs. We find that plasmon-exciton polaritons9 (PEPs) substantially increase the strength of the Purcell effect and achieve an average Purcell factor (PF) of 2.4 ± 0.2 over a 50-nm-thick emission layer (EML) in a blue PHOLED. A 5.3-fold improvement in LT90 (the time for the PHOLED luminance to decay to 90% of its initial value) of a cyan-emitting Ir-complex device is achieved compared with its use in a conventional PHOLED. Shifting the chromaticity coordinates to (0.14, 0.14) and (0.15, 0.20) into the deep blue, the Purcell-enhanced devices achieve 10-14 times improvement over similarly deep-blue PHOLEDs, with one structure reaching the longest Ir-complex device lifetime of LT90 = 140 ± 20 h reported so far10-21. The polariton-enhanced Purcell effect and microcavity engineering provide new possibilities for extending deep-blue PHOLED lifetimes.

Nanoscale Manipulation of Exciton-Trion Interconversion in a MoSe2 Monolayer via Tip-Enhanced Cavity-Spectroscopy.

Emerging light-matter interactions in metal-semiconductor hybrid platforms have attracted considerable attention due to their potential applications in optoelectronic devices. Here, we demonstrate plasmon-induced near-field manipulation of trionic responses in a MoSe2 monolayer using tip-enhanced cavity-spectroscopy (TECS). The surface plasmon-polariton mode on the Au nanowire can locally manipulate the exciton (X0) and trion (X-) populations of MoSe2. Furthermore, we reveal that surface charges significantly influence the emission and interconversion processes of X0 and X-. In the TECS configuration, the localized plasmon significantly affects the distributions of X0 and X- due to the modified radiative decay rate. Additionally, within the TECS cavity, the electric doping effect and hot electron generation enable dynamic interconversion between X0 and X- at the nanoscale. This work advances our understanding of plasmon-exciton-hot electron interactions in metal-semiconductor-metal hybrid structures, providing a foundation for an optimal trion-based nano-optoelectronic platform.

Excitonic Quantum Coherence in Light Emission from CsPbBr3 Metal-Halide Perovskite Nanocrystals.

The decay of excited states via radiative and nonradiative paths is well understood in molecules and bulk semiconductors but less so in nanocrystals. Here, we perform time-resolved photoluminescence (t-PL) experiments on CsPbBr3 metal-halide perovskite nanocrystals, with a time resolution of 3 ps, sufficient to observe the decay of both excitons and biexcitons as a function of temperature. The striking result is that the radiative rate constant of the single exciton increases at low temperatures with an exponential functional form, suggesting quantum coherent effects with dephasing at high temperatures. The opposing directions of the radiative and nonradiative decay rate constants enable enhanced brightening of PL from excitons to biexcitons due to quantum effects, promoting a faster approach to the quantum theoretical limits of light emission. Ab initio quantum dynamics simulations reproduce the experimental observations of radiation controlled by quantum spatial coherence enhanced at low temperatures.

Radiative impacts of the Australian bushfires 2019–2020 – Part 2: Large-scale and in-vortex radiative heating

Abstract. Record-breaking wildfires ravaged south-eastern Australia during the fire season 2019–2020. The intensity of the fires reached its paroxysmal phase at the turn of the year 2019–2020, when large pyro-cumulonimbi developed. Pyro-convective activity injected biomass burning aerosols and gases in the upper-troposphere–lower-stratosphere (UTLS), producing a long-lasting perturbation to the atmospheric composition and the stratospheric aerosol layer. The large absorptivity of the biomass burning plume produced self-lofting of the plume and thus modified its vertical dynamics and horizontal dispersion. Another effect of the in-plume absorption was the generation of compact smoke-charged anticyclonic vortices which ascended up to 35 km altitude due to diabatic heating. We use observational and modelling description of this event to isolate the main vortex from the dominant Southern Hemispheric biomass burning aerosol plume. Entering this information into an offline radiative transfer model, and with hypotheses on the absorptivity and the angular scattering properties of the aerosol layer, we estimate the radiative heating rates (HRs) in the plume and the vortex. We found that the hemispheric-scale plume produced a HR of 0.08±0.05 K d−1 (from 0.01 to 0.15 K d−1, depending on the assumption on the aerosol optical properties), as a monthly average value for February 2020, which is strongly dependent on the assumptions on the aerosol optical properties and therefore on the plume ageing. We also found in-vortex HRs as large as 15–20 K d−1 in the denser sections of the main vortex (8.4±6.1 K d−1 on average in the vortex). Our results suggest that radiatively heated ascending isolated vortices are likely dominated by small-sized strongly absorbing black carbon particles. The hemispheric-scale and in-vortex HR estimates are consistent with the observed ensemble self-lofting (a few kilometres in 4 months) and the main isolated vortex rise (∼ 20 km in 2 months). Our results also show evidence of the importance of longwave emission in the net HR of biomass burning plumes.

Calculation of Thermalized Component of Neutron Spectra in a D-D Neutron Generator

The results of the thermalized flux calculation that incorporate radiative capture reactions in the presence and absence of polyethylene blocks that form an enclosure for a deuteron-deuteron (D-D) neutron generator are presented. This method can be used to measure the moderated neutron flux component in a mixture of moderated and primary neutron spectra. Using 20-cm-thick polyethylene blocks to surround a D-D neutron generator, the moderation of primary neutrons was investigated using nine indium foils. In this paper, the relationship between the moderated neutron flux and the radiative capture rates in the presence and absence of polyethylene blocks is derived. This is compared to a MCNP simulation and a calculation of modulated flux that ignore the primary neutron components.

Strongly Luminescent Tetradentate Palladium(II)‐TADF Emitters. Blue TADF And TADF‐Sensitized OLEDs with External Quantum Efficiencies Over 23%

AbstractDue to the low‐lying Pd(4d)‐orbitals, luminescent palladium(II) complexes usually show 3IL phosphorescence (IL = intraligand) with excited state lifetimes in the range of hundreds of microseconds, which limits their application in blue organic light‐emitting diodes (OLEDs). Here, a molecular design strategy for the development of strongly luminescent Pd(II)‐based thermally activated delayed fluorescence (TADF) emitters with fast radiative decay rate constants and reverse intersystem crossing rate (kRISC) constants is presented. The synthesized tetradentate [Pd(N*C*C^N)] TADF emitters show sky‐blue to yellow (λmax = 484–565 nm) emission with excited state lifetimes in the range of 0.9−8.7 µs and high photoluminescence quantum yield of up to 77% in CH2Cl2 solution. In 5 wt.% 2,8‐bis(diphenylphosphoryl)dibenzo[b,d]furan (PPF) thin films, these [Pd(N*C*C^N)] TADF complexes display blue to sky‐blue (476−496 nm) emission with quantum yields close to unity. Variable‐temperature emission lifetime measurements, femtosecond time‐resolved spectroscopy, and density functional theory (DFT) and time‐dependent DFT (TDDFT) calculations together reveal ultrafast kRISC rate constants of these [Pd(N*C*C^N)] TADF emitters. Using these Pd(II)‐TADF emitters as dopants, sky‐blue TADF and blue TADF‐sensitized OLEDs with small efficiency roll‐offs achieved high maximum external quantum efficiencies (EQEs) of 24.8% and 23.1%, respectively.

Molecular Engineering Modulating the Singlet-Triplet Energy Splitting of Indolocarbazole-Based TADF Emitters Exhibiting AIE Properties for Nondoped Blue OLEDs with EQE of Nearly 20.

The development of efficient blue thermally activated delayed fluorescence (TADF) emitters with an aggregation-induced emission (AIE) nature, for the construction of organic light-emitting diodes (OLEDs), is still insufficient. This can be attributed to the challenges encountered in molecular design, including the inherent trade-off between radiative decay and reverse intersystem crossing (RISC), as well as small singlet-triplet energy splitting (ΔEST) and the requirement for high photoluminescence quantum yields (ΦPL). Herein, we present the design of three highly efficient blue TADF molecules with AIE characteristics by combining π-extended donors with different acceptors to modulate the differences in the electron-donating and electron-withdrawing abilities. This approach not only ensures high emission efficiency by suppressing close π-π stacking, weakening nonradiative relaxation, and enhancing radiative transition but also maintains the equilibrium ratio between the triplet and singlet excitons by facilitating the process of RISC. These emitters exhibit AIE and TADF properties, featuring quick radiative rates and low nonradiative rates. The ΦPL of these emitters reached an impressive 88%. Based on their excellent comprehensive performance, nondoped PICzPMO and PICzPMO OLEDs achieved excellent electroluminescence performance, exhibiting maximum external quantum efficiency (EQEmax) of up to 19.5%, while the doped device achieved a higher EQEmax of 20.8%. This work demonstrated that by fusing π-extended large rigid donors with different acceptors, it is possible to regulate the difference in electron-donating and electron-withdrawing abilities, resulting in a small ΔEST, high ΦPL, and fast RISC process, which is a highly feasible strategy for designing efficient TADF molecules.

An A-D-A-Type Thermally Activated Delayed Fluorescence Emitter with Intrinsic Yellow Emission Realizing Record-High Red/NIR OLEDs upon Modulating Intermolecular Aggregations.

Realizing efficient red/near-infrared (NIR) electroluminescence (EL) by precisely modulating molecular aggregations of thermally activated delayed fluorescence (TADF) emitters is an attractive pathway, yet the molecular designs are elusive. Here, a new approach is proposed to manage molecular aggregation via a mild-twist acceptor-donor-acceptor (A-D-A)-type molecular design. A proof-of-concept TADF molecule, QCN-PhSAC-QCN, is developed that furnishes a fast radiative rate and obvious aggregation-induced emission feature. Its emission bands can be facilely shifted from intrinsic yellow to the red/NIR region via fine-tuning doping levels and molecular aggregates while maintaining elegant photoluminescence quantum yields benefiting from suppressed exciton annihilation processes. As a result, a QCN-PhSAC-QCN-based organic light-emitting diode (OLED) exhibits a record-setting external quantum efficiency (EQE) of 39.1% at a doping ratio of 10wt.%, peaking at 620nm. Moreover, its nondoped NIR OLED affords a champion EQE of 14.3% at 711nm and retains outstanding EQEs of5.40% and 2.35% at current densities of 10 and 100 mA cm-2 , respectively, which are the highest values among all NIR-TADF OLEDs at similar density levels. This work validates the feasibility of such mild-twist A-D-A-type molecular design for precisely controlling molecular aggregation while maintaining high efficiency, thus providing a promising pathway for high-performance red/NIR TADF OLEDs.

Concentration- and temperature- dependent luminescence quenching and optical transition of Sr2GdTaO6: Eu3+ phosphor for potential applications in white LEDs

A series of Eu3+ doped Sr2GdTaO6 (SGT) phosphors with double perovskite structure were synthesized via a high-temperature solid-state reaction approach. The crystal structure, morphology and luminescence properties were characterized by means of X-ray diffraction, transmission electron microscope, luminescence spectroscopy and fluorescence decay lifetimes, respectively. Under the excitation of 394 nm, intense red emission in the visible region was observed in Eu3+ doped SGT phosphors, and the critical quenching concentration of Eu3+ in SGT phosphors was derived to be 15 mol%. The chromaticity coordinates and color purity of SGT: 15 mol% Eu3+ were calculated to be (0.61, 0.36) an 93.82 %, respectively. Meanwhile, it was also confirmed that the electric quadrupole–quadrupole interaction is responsible for the luminescence concentration quenching of Eu3+. The internal quantum efficiency of SGT: Eu3+ phosphors with different Eu3+ concentrations were calculated. Furthermore, the crossover process was confirmed to be the main mechanism for luminescence thermal quenching based on the temperature-dependent emission spectra and temperature-dependent fluorescence lifetimes. In addition, the Judd-Ofelt parameters, radiative transition rates and branch ratios from the 5D0 emitting states to various lower energy states were evaluated with the aid of the Judd-Ofelt theory, respectively. All results indicate that SGT: Eu3+ samples are a promising red-emitting phosphor.

Enhancing Multiexcitonic Emission in Metal-Halide Perovskites by Quantum Confinement.

Semiconductor metal halide perovskite nanocrystals have been under intense investigation for their promise in a variety of optoelectronic applications, which arises from their remarkable properties of defect tolerance and efficient light emission. Recently, quantum dot versions of perovskite nanocrystals have been available, enabling investigation of how quantum size effects control optical function and performance in these quantum dots (QD), past their well-known covalent II-VI analogues. We perform time-resolved photoluminescence (t-PL) experiments on CsPbBr3 perovskite nanocrystals spanning in diameter from 5.8 nm strongly confined quantum dots to 18 nm weakly confined quantum dots. Experiments are performed with sufficient time resolution of 3 ps to observe the interaction energies and recombination kinetics from excitons to multiexcitons. Comparing the same sized QD reveals that perovskite QD have a larger radiative rate constant for emission from X than CdSe QD due to a larger oscillator strength. The multiexciton (MX) regime reveals that perovskite QD emit brightly and with more focused bandwidth than equivalent sized CdSe QD enabling more spectrally pure brightness. The MX kinetics reveals that the perovskite QD maintain efficient radiative decay, effectively competing with Auger recombination. These experiments reveal that the strongly confined QD of perovskites can be efficient multiexcitonic emitters, such as in high brightness light emitting diodes, especially in the blue.

Cationic Porphyrin-Based Ionic Nanomedicines for Improved Photodynamic Therapy.

This study presents the synthesis and characterization of monosubstituted cationic porphyrin as a photodynamic therapeutic agent. Cationic porphyrin was converted into ionic materials by using a single-step ion exchange reaction. The small iodide counteranion was replaced with bulky BETI and IR783 anions to reduce aggregation and enhance the photodynamic effect of porphyrin. Carrier-free ionic nanomedicines were then prepared by using the reprecipitation method. The photophysical characterization of parent porphyrin, ionic materials, and ionic nanomaterials, including absorbance, fluorescence and phosphorescence emission, quantum yield, radiative and nonradiative rate, and lifetimes, was performed. The results revealed that the counteranion significantly affects the photophysical properties of porphyrin. The ionic nanomaterials exhibited an increase in the reactive oxygen yield and enhanced cytotoxicity toward the MCF-7 cancer cell line. Examination of results revealed that the ionic materials exhibited an enhanced photodynamic therapeutic activity with a low IC50 value (nanomolar) in cancerous cells. These nanomedicines were mainly localized in the mitochondria. The improved light cytotoxicity is attributed to the enhanced photophysical properties and positive surface charge of the ionic nanomedicines that facilitate efficient cellular uptake. These results demonstrate that ionic material-based nanodrugs are promising photosensitizers for photodynamic therapy.

A Rigid Multiple Resonance Thermally Activated Delayed Fluorescence Core Toward Stable Electroluminescence and Lasing.

The investigation of organic light-emitting diodes (OLEDs) and organic laser devices with thermally activated delayed fluorescence (TADF) molecules is emerging due to the potential of harnessing triplets. In this work, a boron/nitrogen multiple-resonance TADF polycyclic framework fusing carbazole units (CzBNPh) was proposed. CzBNPh exhibited a narrowband emission (<30 nm), a unity photoluminescence quantum yield, and a fast radiative rate. Consequently, CzBNPh demonstrated a low distributed feedback (DFB) lasing threshold of 0.68 μJ cm-2 . Furthermore, the stimulated emission zone of CzBNPh was effectively separated from its singlet and triplet absorption, thereby minimizing the singlet-triplet annihilation under long-pulsed excitation ranging from 20 μs to 2.5 ms. Significantly, the enhanced rigid molecular conformation, thermal stability, and photo-stability resulted in improved lasing and electroluminescence stability compared to that of 5,9-diphenyl-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene (DABNA)-core. These findings indicate the potential of CzBN-core as a promising framework for achieving long-pulsed wave and electrically-pumped lasing in the future.