Time-resolved Emission Spectroscopy Research Articles

An iridium(III) complex-based luminogenic probe for high-throughput screening of hydrogen sulfide donors in living cells.

The scarcity of suitable high-throughput screening technology for hydrogen sulfide (H2S) donors has hampered the discovery of H2S donors. In this study, a long-lived cyclometalated iridium complex was rationally designed as a mitochondria-targeted H2S probe to monitor the real-time dynamic change of H2S. By using the time-resolved emission spectroscopy (TRES) technique, an anti-interference high-throughput screening system was developed to monitor H2S in living cells with decreased false negative results. As a proof-of-concept, three natural products were identified as potential H2S donors from a natural product library using the developed TRES probe. Notably, the discovery of allicin and diallyl trisulfide demonstrated the feasibility of this screening platform, while garlic-derived allyl methyl sulfide was explored as a H2S donor candidate. The results were further validated by a commercial assay. We anticipate this high-throughput platform could facilitate the discovery of H2S donors by discriminating the endogenous interfering fluorescence from biological systems.

Reassessing the Photochemical Upcycling of Polystyrene Using Acridinium Salts.

Approaches aimed at deconstructing PS by photocatalytic means struggle to generate high-energy species capable of cleaving the C-H and C-C bonds of PS. We show herein that 9-mesityl-10-methylacridinium perchlorate (MA) is capable of upcycling various grades of PS susbstrates into benzoic acid (BAc) up to 40%, with small proportions of acetophenone and formic acid, under visible light (456 nm) or through solar radiation. Time-resolved emission and absorption spectroscopy evidence that a reaction with oxygen is the primary photochemical step in oxygen-saturated solutions, accounting for 77% of the photons absorbed vs. 1% for the direct reaction with PS. These results suggest a mechanism in which MA-mediated photocycling of PS to BAc occurs through the abstraction of benzylic H atoms by reactive oxygen species generated by energy or electron transfer from the excited state of MA. Addition of triplet O2 to these radicals, followed by intra- or inter-molecular hydrogen atom transfer (HAT), generates C- or O-centered radicals then undergoing β-scission or hydroperoxide fragmentation. The formation of intermediate oligomers functionalized by terminal carbonyl groups is demonstrated by both infrared analysis and mass spectrometry. These oligomers undergo further photoinduced conversion in the absence of MA, as evidenced by size exclusion chromatography analysis.

An Increase in the Rigidity of the Environment Favors MLCT over the MC State in [Ru(bpy)2(Nicotine)2](Cl)2: A Case Study of Photolabile Ligands.

Ru(II)-complexes with photolabile ligands find a wide range of applications, e.g., in drug release and in the design of light-responsive interfaces. While light-driven ligand loss has been studied mechanistically in detail for complexes in solution, comparably few studies are present that investigate the process in a material context, i.e., in a rigid environment and in the absence of solvent. This paper adds to this underrepresented perspective by studying the excited-state dynamics of [Ru(bpy)2(nicotine)2] (Cl)2 (Ru-nico) as a model system in poly(methyl methacrylate) (PMMA) and polyacrylonitrile (PAN) matrices. Femtosecond transient absorption spectroscopy and time-resolved emission spectroscopy are employed to monitor the photodissociation of labile nicotine ligands in polymer environments. Photoexcitation within the metal-to-ligand charge transfer (MLCT) band leads to transient dissociation of the nicotine ligand when the complex is dissolved in water. However, optical excitation of the 1MLCT transition of the complexes embedded in polymer matrices does not result in photodissociation, likely due to the rigidity of the environment, which cannot solvate the undercoordinated complex after ligand dissociation and the dissociated ligand. These insights shed light on the role of the local environment when considering the photophysics of ligand loss from Ru(II)-polypyridyl complexes and, hence, their use in the light-activation of reactive molecular components in materials.

Electrical and optical characteristics of a nanosecond pulsed electrical discharge in air in contact with a water droplet for various electrical conductivities

Abstract Interactions between pulsed electrical discharges and liquid dielectric materials is a growing research field with interests in fundamental discharge physics as well as in applications. Herein, we present an experimental study on the dynamics of nanosecond discharges in air with the presence of a water droplet with various electrical conductivities (EC) and at different applied voltages (Va). The discharges are characterized optically, by employing time-resolved ICCD imaging and optical emission spectroscopy, as well as electrically, by acquiring the current-voltage waveforms for every discharge. The results show that three modes of discharges can be obtained: i) streamer discharge between the cathode and the droplet, ii) streamer discharge between the cathode and the droplet as well as between the anode and the droplet, and iii) spark discharge that connects the two electrodes and propagates over the droplet. We find that the probability to obtain one of the three discharge modes is strongly related to the droplet’s EC as well as to Va. Although the ignition of the streamer is relatively insensitive to EC, its transition to a spark can be finely controlled by the droplet’s EC. The time-resolved ICCD images show that the discharge initiates in the gap between the cathode and the droplet, followed by ignition between the anode/ground electrode and the droplet. Then, an extinction phase is observed before the ignition of a secondary streamer, and depending on the conditions, the discharge may transition to a spark, i.e. a channel with high emission intensity. We find that the duration of each stage of discharge propagation as well as the corresponding emission (path and intensity) are sensitive to droplet’s EC. Finally, emissions from streamers (primary and secondary) as well as from sparks are analyzed using optical spectroscopy. We find that the emission from the streamers is dominated by the second positive system of N2, and that the droplet’s EC does not significantly influence the emission spectra nor the estimated rotational temperature of N2.

Monovalent nickel ion as ionization probe in matrix-assisted laser desorption/ionization mass spectrometry

We have developed NiO/HM20, a matrix composed of NiO nanoparticles (NiO) loaded on zeolite surface, for matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS). By photoexcitation, monovalent nickel ion (Ni+) was dominantly observed with high intensity. The mechanism of Ni+ production was studied by picosecond time-resolved emission spectroscopy. By loading NiO on the zeolite surface, a new relaxation pathway to other electronic excited states was observed, which increased the lifetime of electron–hole pairs and promoted the reduction of nickel. The long-lived charge-separated electronic excited state corresponding to the large polarization of NiO was confirmed by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction spectroscopy (XRD). The correlation between the Auger parameter related to the polarization energy and the Ni+ peak intensity in the mass spectrum was confirmed. By applying the developed NiO/HM20 matrix to the MS measurement of small molecules, we found that molecules were ionized through complex formation with Ni+ using the coordination of lone electron pairs or π-electrons in the analyte molecules.

Controlled Photooxidation via Singlet Oxygen Generation by Triplet Harvesting in a Heavy Atom Free Pure Organic Dithienylethene-Naphthalene Diimide.

Noninvasive control over the reversible generation of singlet oxygen (1O2) has found the enormous practical implications in the field of biomedical science. However, metal-free pure organic emitters, connected with a photoswitch, capable of generating "on-demand" 1O2 via triplet harvesting remain exceedingly rare; therefore, the utilization of these organic materials for the reversible control of singlet oxygen production remains at its infancy. Herein, an ambient triplet mediated emission in quinoline-dithienylethene (DTE)-core-substituted naphthalene diimide (cNDI) derivative is unveiled via delayed fluorescence. The quinoline-DTE-cNDI triad displayed enhanced photoswitching efficiency via double FRET mechanism. It was found to have direct utilization in controlled photosensitized organic transformations via efficient generation of singlet oxygen (yield ΦΔ~0.55 in DCM and 0.73 in methanol). The designed molecule exhibits a long-lived emission (τ∼1.1 μs) and very small singlet-triplet splitting (ΔEST) of 0.13 eV empowering it to display delayed fluorescence. Comprehensive steady state and time-resolved emission spectroscopy (TRES) analyses along with DFT calculations offer detailed understandings into the excited-state manifolds of organic compound and energy transfer (ET) pathways involved in 1O2 generation.

Synthesis and Characterization of Aromatic Heterocycle-Fused Porphyrins

The advances in materials science increasingly demand novel functionalized materials. Porphyrins fused with aromatic moieties represent attractive largely π-extended structures, offering new opportunities in molecular and organic electronics.1-4 In this presentation, new synthetic methods to fuse different type of aromatic rings to the porphyrin periphery will be presented. These new methods have led to the synthesis of novel large π-extended molecular structures incorporating both porphyrins and other aromatic components including acenaphtho[1,2-b]pentacene-, acenaphtho[1,2-b]pentacene quinone, benzodithiophenes and cyclooctatetraenes. Unprecedented electronic and photophysical properties have discovered for these π-extended porphyrins. For example, an unusual trend was observed in the florescence quantum yield upon converting thiophene-attached benzoporphyrin to naphthodithiophene-fused porphyrin. A remarkable light effect was obtained with a acenaphtho[1,2-b]pentacene-fused porphyrin-phthalocyanine heterojunction device, which exhibited high ammonia sensitivity. The characterizations of these π-extended porphyrins including time-resolved emission and transient absorption spectroscopy, cyclic voltammetry, DFT calculations will also be presented. Reference Stepien, E. Gonka, M. Zyla and N. Sprutta, Chem. Rev., 2017, 117, 3479-3716.Narita, X. Y. Wang, X. Feng and K. Mullen, Chem. Soc. Rev., 2015, 44, 6616-6643.P. Lewtak and D. T. Gryko, Chem. Commun., 2012, 48, 10069-10086.K. S. Davis, A. L. Thompson and H. L. Anderson, J. Am. Chem. Soc., 2011, 133, 30-3.Hu, M. B. Thomas, W. A. Webre, A. Moss, R. G. W. Jinadasa, V. N. Nesterov, F. D’Souza and H. Wang, Angew. Chem. Int. Ed., 2020, 45 (132), 20250-20257.Moss, Y. Jang, J. Arvidson, V. N. Nesterov, F. D’Souza and H. Wang, Chem. Sci., 2022, 13, 9880 -9890.Moss, D. E. Nevonen, Y. Hu, V. N. Nesterov, V. Nemykin and H. Wang*, ACS Phys. Chem. Au, 2022, 2, 6, 468-481.Washburn, R. Kaswan, S. Shaikh, A. Moss, F. D’Souza and Hong Wang, J. Phys. Chem. A., 2023,127 (43):9040-9051.Cooper, A. Alsaleh, S. Kumar, W. Rackers, V. N. Nesterov, F. D’Souza, S. A. Vinogradov and H. Wang, Chem. Eur. J., 2023, e202302013.Moss, Y. Jang, H. Wang, F. D’Souza, ChemSusChem, 2023, 16 (8), e202202289.

Revealing the ESIPT process in benzoxazole fluorophores within polymeric matrices through theory and experiment.

The impact of the polymeric matrix on the photophysical characteristics of monomeric dyes responsive to excited-state intramolecular proton transfer (ESIPT) was investigated through UV-Vis absorption as well as steady-state and time-resolved emission spectroscopies. For this purpose, two benzoxazole monomers (M1 and M2) with acryloyl groups at different positions in their molecular structures were employed to facilitate covalent bonding within a styrene chain. Our findings reveal significant variations in their excited-state properties due to the proximity of the acryloyl groups, which affects the energy barrier of the ESIPT reaction, the emission wavelength, and the balance between the normal and tautomeric forms. The experimental results were corroborated through theoretical investigations at the DFT/TDDFT level, specifically using the B3LYP-D3/def2-TZVP methodology. Three notable observations emerged: donor/acceptor groups at the meta/para positions induced electron distribution changes, causing red-shifted emission for M2; in the polymer film, particularly in PM1, intramolecular hydrogen bond deactivation favored N* emission over T* emission; and the zwitterionic character of the T* species. This study underscores the advantages of functionalization in polymers, which can lead to colorless films and prevalent N* or T* emission, and contributes valuable insights into molecular design strategies for tailoring the photophysical properties of polymeric materials.

Time-Resolved X-ray Emission Spectroscopy and Resonant Inelastic X-ray Scattering Spectroscopy of Laser Irradiated Carbon.

The existence of liquid carbon as an intermediate phase preceding the formation of novel carbon materials has been a point of contention for several decades. Experimental observation of such a liquid state requires nonthermal melting of solid carbon materials at various laser fluences and pulse properties. Reflectivity experiments performed in the mid-1980s reached opposing conclusions regarding the metallic or insulating properties of the purported liquid state. Time-resolved X-ray absorption studies showed shortening of C-C bonds and increasing diffraction densities, thought to evidence a liquid or glassy carbon state, respectively. Nevertheless, none of these experiments provided information on the electronic structure of the proposed liquid state. Herein, we report the results of time-resolved resonant inelastic X-ray scattering (RIXS) and time-resolved X-ray emission spectroscopy (XES) studies on amorphous carbon (a-C) and ultrananocrystalline diamond (UNCD) as a function of delay time between the irradiating pulse and X-ray probe. For both a-C and UNCD, we attribute decreases in RIXS or XES signals to transition blocking, relaxation, and finally, ablation. Increased signal at 20 ps following the irradiation of the UNCD is attributed to the probable formation of nanoscale structures in the ablation plume. Differences in the amount of signal observed between a-C and UNCD are explained by the difference in sample thickness and, specifically, incomplete melting of the UNCD film. Comparisons to spectral simulations based on MD trajectories at extreme conditions indicate that the carbon state in our experiments is crystalline. Normal mode analysis confirmed that symmetrical bending or stretching of the C-C bonds in the diamond lattice results in XES spectra with small intensity differences. Overall, we observed no evidence of melting to a liquid state, as determined by the lack of changes in the spectral properties for up to 100 ps delays following the melting pulses.

Time-Resolved X-ray Emission Spectroscopy and Synthetic High-Spin Model Complexes Resolve Ambiguities in Excited-State Assignments of Transition-Metal Chromophores: A Case Study of Fe-Amido Complexes.

To fully harness the potential of abundant metal coordination complex photosensitizers, a detailed understanding of the molecular properties that dictate and control the electronic excited-state population dynamics initiated by light absorption is critical. In the absence of detectable luminescence, optical transient absorption (TA) spectroscopy is the most widely employed method for interpreting electron redistribution in such excited states, particularly for those with a charge-transfer character. The assignment of excited-state TA spectral features often relies on spectroelectrochemical measurements, where the transient absorption spectrum generated by a metal-to-ligand charge-transfer (MLCT) electronic excited state, for instance, can be approximated using steady-state spectra generated by electrochemical ligand reduction and metal oxidation and accounting for the loss of absorptions by the electronic ground state. However, the reliability of this approach can be clouded when multiple electronic configurations have similar optical signatures. Using a case study of Fe(II) complexes supported by benzannulated diarylamido ligands, we highlight an example of such an ambiguity and show how time-resolved X-ray emission spectroscopy (XES) measurements can reliably assign excited states from the perspective of the metal, particularly in conjunction with accurate synthetic models of ligand-field electronic excited states, leading to a reinterpretation of the long-lived excited state as a ligand-field metal-centered quintet state. A detailed analysis of the XES data on the long-lived excited state is presented, along with a discussion of the ultrafast dynamics following the photoexcitation of low-spin Fe(II)-Namido complexes using a high-spin ground-state analogue as a spectral model for the 5T2 excited state.

Poly(2-Oxazoline) Amphiphilicity Tunes the Excited-State Proton Transfer of Pyrenol-Based Polyphotoacids.

The ability of light to change the properties of light-responsive polymers opens avenues for targeted release of cargo with a high degree of spatial and temporal control. Recently, we established photoacid polymers as light-switchable macromolecular amphiphiles. In these systems, light-induced excited-state proton transfer (ESPT) causes changes in amphilicity. However, as the intermolecular process itself critically depends on the local environment of the photoacid unit within the polymer, the overall amphiphilicity directly influences ESPT. Thus, understanding the impact of the local environment on the photophysics of photoacidic side chains is key to material design. In this contribution we address both thermodynamic and kinetic aspects of ESPT in oxazoline-based amphiphilic polymers with pyrenol-based photoacid side chains. We will compare the effect of polymer design, i. e. statistical and block arrangements, i. e. in poly[(2-ethyl-2-oxazoline)-co-(1-(6/8-hydroxyperene)sulphonylaziridine)] and poly(2-ethyl-2-oxazoline)-block-poly[(2-ethyl-2-oxazoline)-co-(2-(3-(6-hydroxypyrene)sulphonamide)propyl-2-oxazoline), on the intermolecular proton transfer reaction by combining steady-state and time-resolved absorption and emission spectroscopy. ESPT appears more prominent in the statistical copolymer compared to a block copolymer with overall similar pyrenol loading. We hypothesize that the difference is due to different local chain arrangements adopted by the polymers in the two cases.

A comparative study on the spectral characteristics of nanosecond pulsed discharges in atmospheric He and a He+2.3%H2O mixture

Nanosecond pulsed discharges at atmospheric pressure in a pin-to-pin electrode configuration are well reproducible in time and space, which is beneficial to the fundamentals and applications of low-temperature plasmas. In this experiment, the discharges in helium (He) and He with 2.3% water vapor (H2O) are driven by a series of 10 ns overvoltage pulses (~13 kV). Special attention is paid to the spectral characteristics obtained in the center of discharges by time-resolved optical emission spectroscopy. It is found that in helium, the emission of atomic and molecular helium during the afterglow is more intense than that in the active discharge, while in the He+2.3%H2O mixture, helium emission is only observed during the discharge pulse and the molecular helium emission disappears. In addition, the emissions of OH(A-X) and Hα present similar behavior that increases sharply during the falling edge of the voltage pulse as the electrons cool down rapidly. The gas temperature is set to remain low at 540 K by fitting the OH(A-X) band. A comparative study on the emission of radiative species (He, He2, OH and H) is performed between these two discharge cases to derive their main production mechanisms. In both cases, the dominant primary ion is He+ at the onset of discharges, but their He+ charge transfer processes are quite different. Based on these experimental data and a qualitative discussion on the discharge kinetics, with regard to the present discharge conditions, it is shown that the electron-assisted three-body recombination processes appear to be the significant sources of radiative OH and H species in high-density plasmas.

Photophysical Studies of a Zr(IV) Complex with Two Pyrrolide-Based Tetradentate Schiff Base Ligands.

The reaction of two equivalents of N,N'-bis(2-pyrrolylmethylidene)-1,2-phenylenediamine (H2bppda) with tetrabenzylzirconium provided the air- and moisture-stable eight-coordinate complex Zr(bppda)2. Temperature-dependent steady-state and time-resolved emission spectroscopy established weak photoluminescence (ΦPL = 0.4% at 293 K) by a combination of prompt fluorescence and thermally activated delayed fluorescence (TADF) upon visible light excitation at and around room temperature. TADF emission is strongly quenched by 3O2 and shows highly temperature-sensitive emission lifetimes of hundreds of microseconds. The lifetime of the lowest energy singlet excited state, S1, was established by transient absorption spectroscopy and shows rapid deactivation (τ = 142 ps) by prompt fluorescence and intersystem crossing to the triplet state, T1. Time-dependent density functional theory (TD-DFT) calculations predict moderate ligand-to-metal charge transfer (LMCT) contributions of 25-30% for the S1 and T1 states. A comparison of Zr(bppda)2 to related zirconium pyridine dipyrrolide complexes, Zr(PDP)2, revealed important electronic structure changes due to the eight-coordinate ligand environment in Zr(bppda)2, which were correlated to differences in the photophysical properties between the two compound classes.

Influence of the RF voltage amplitude on the space- and time-resolved properties of RF–LF dielectric barrier discharges in α–γ mode

This work reports the results of an experimental and modeling study on dual-frequency Ar–NH3 dielectric barrier discharges (DBDs) exhibiting the α–γ transition. A combination of space- and time-resolved optical absorption and emission spectroscopy is used to record spatio-temporal mappings of the Ar metastable number density, Ar 750.4 nm line emission intensity, and electron–Ar bremsstrahlung continuum emission intensity. With the increase of the radio frequency (RF) voltage amplitude in a 50 kHz–5 MHz DBD, maximum populations of Ar excited species (1s and 2p states, linked to the population of high-energy electrons) observed in the γ mode decrease and appear earlier in the low-frequency cycle. On the other hand, the density of the bulk electrons, monitored from the continuum emission intensity, increases, with a more prominent rise in the RF-α mode than in the γ regime. Such behaviors are consistent with the predictions of 1D fluid model and results from a decrease of the gas voltage required for self-maintenance of the cathode sheath in the γ breakdown.

Dual-frequency sheath oscillations and consequences on the ion and electron transport in dielectric barrier discharges at atmospheric pressure

Current–voltage characteristics, space- and time-resolved optical emission spectroscopy, and 1D fluid modeling are used to examine the effect of dual-frequency sheath oscillations on the ion and electron transport in dielectric barrier discharges sustained by a combination of low frequency (LF, 50 kHz, 650 V) and radiofrequency (RF, 5.3 MHz, 195 V) voltages, exhibiting the α-to-γ mode transition. On one hand, when polarities of the LF and RF voltages are opposite, an electric field near the LF cathode (due to LF cathode sheath) drives the secondary electrons to the plasma bulk and an opposite electric field between the sheath edge and the LF anode attracts the electrons toward the LF cathode (to maintain quasi-neutrality in the plasma bulk). At the sheath edge, electrons become trapped and ions drift toward the cathode and the anode simultaneously according to their position in the gap. On the other hand, when the RF voltage has the same polarity as the LF voltage, the total applied voltage increases and this yields to enhanced production of electrons and ions in the sheath. To maintain quasi-neutrality in the bulk, the electric field along the gap exhibits the same polarity as the one in the sheath, allowing electrons created in the sheath to be evacuated toward the LF anode. The behavior of the LF cathode is, therefore, controlled by the LF sheath, and, thus, by the LF voltage amplitude, while the behavior in the bulk and at the anode alternates on the time scale of the RF voltage.

Layer-by-layer structured nanocomposite deposits from plasma-synthesized organosilicon nanoparticles and organosilicon nanoparticles decorated with Ag nanoparticles by taking advantage of cyclic nanoparticle formation in Ar/HMDSO reactive plasmas

Rational engineering of thin nanocomposite layers, deposited in reactive plasmas, requires knowledge on the plasma behavior in order to produce multifunctional deposits with tailored properties (structural, optical, electrical, etc.) This work presents an experimental study of nanoparticles synthesized in the plasma gas-phase and their subsequent use as building-blocks to form layer-by-layer nanostructures. The experiment is performed in a plasma process that successfully combines plasma polymerization of an organosilicon molecular precursor (hexamethyldisiloxane, HMDSO) and sputtering of a metallic (silver) target. Pulsed injection of the precursor is found to promote cyclic nanoparticle formation in Ar/HMDSO reactive plasmas. The plasma electron temperature is found to vary in the range 1.6—2.2 eV as derived from time-resolved optical emission spectroscopy of the plasma energetic conditions. This diagnostic method is also shown to provide a reliable tool for online monitoring of the nanoparticle synthesis process. Two types of layer-by-layer structured nanocomposites can be obtained depending on the type of nanoparticles synthesized: (i) organosilicon nanoparticles of size less than 100 nm in all studied plasma conditions for a large quantity of injected HMDSO and (ii) raspberry-like nanoparticles of size less than 150 nm when the quantity of injected HMDSO is reduced. The organosilicon nanoparticle growth follows a polydimethylsiloxane (PDMS)-like oligomerization scheme in which the R2-Si(-O)2 silicon bond tends towards the formation of polymeric structure in a R3-Si(-O)1 silicon chemical environment, containing Si-(CH2)-Si type bridges that are involved in cross-linking. The elemental composition of the raspberry-like nanoparticles is similar to that of the organosilicon nanoparticles, supplemented by the Ag component. The decorating silver nanoparticles are ∼15 nm of size, round in shape and polycrystalline. There is no evidence for silver oxides in the nanostructures. The Si-O-Ag bridges, revealed by infrared spectroscopy, suggest the presence of junction sites between the metallic and the organosilicon parts of the raspberry-like nanoparticles. The silver nanoparticles are found to decorate the organosilicon nanoparticles to form the raspberry-like nanoparticles in the plasma gas-phase, before being deposited. This reveals a very interesting phenomenon of simultaneous growth of the silver- and organosilicon-parts in the plasma without mixing during the nucleation phase.

Highly efficient broadband near-infrared luminescence phosphors Ca3MgSn0.5Zr0.5Ge3O12:Pr3+,Cr3+ for multifunctional applications in pc-LEDs field

Exploring high-performance broadband near-infrared (NIR) emitting materials is crucial for the development of NIR devices. In this study, Ca3MgSn0.5Zr0.5Ge3O12:Cr3+ and rare earth ion Pr3+ co-doped Ca3MgSn0.5Zr0.5Ge3O12:Pr3+,Cr3+ phosphors were successfully synthesized. By utilizing time-resolved emission spectroscopy (TRES), photoluminescence (PL) spectra, and fluorescence decay curve, the Ca3MgSn0.5Zr0.5Ge3O12:Cr3+ phosphor is determined to exhibit a broadband emission (650–1150 nm) with a peak at 795 nm due to Cr3+ occupying multiple cationic sites. Ca3MgSn0.5Zr0.5Ge3O12:0.1Cr3+ has excellent thermal stability (86%@425 K), and co-doping Pr3+ ions into Ca3MgSn0.5Zr0.5Ge3O12:0.1Cr3+ obtains highly efficient NIR emission. The Ca3MgSn0.5Zr0.5Ge3O12:0.01Pr3+,0.1Cr3+ phosphor has quantum yield of 89.4% thanks to the energy transfer effect from Pr3+ to Cr3+. The fabricated NIR phosphor-converted light emitting diodes (pc-LEDs) by integrating the blue chip with Ca3MgSn0.5Zr0.5Ge3O12:0.01Pr3+,0.1Cr3+ has diverse applications including night vision, non-destructive testing, and medical imaging.

Spectroscopic investigation of early light emission from anode-initiated surface flashover in vacuum

Time-resolved optical emission spectroscopy is used to explore the early development of anode-initiated flashover in vacuum. An experimental apparatus for collecting flashover self-luminosity is introduced, which enables spatially resolved light collection from regions adjacent to the anode and cathode triple junctions. The emitted light is spectrally and temporally resolved utilizing an imaging spectrograph and a fast electronic shutter camera. The first light detectable from flashovers across both Rexolite and polytetrafluoroethylene (PTFE) insulators begins less than 10 ns prior to the flashover gap's impedance collapse and consists of faint broadband feature in primarily visible wavelengths. This suggests luminosity due to excitation in the solid, possibly occurring as a result of field emitted electrons. In the few nanoseconds leading up to and including the impedance collapse, the broadband spectrum grows in intensity and extends into the UV, eventually accompanied by a few emission lines of the insulator material. This is strong evidence that the early stages of anode-initiated flashover include surface layer breakdown of the insulator, as a contrast from cathode-initiated flashover, which is predominately an above-surface process. Spectra accumulated over longer exposures of PTFE flashovers indicate that, in the first few hundred nanoseconds after the impedance collapse, ions from the insulator material constitute the majority of the emission lines. Later, neutral and ionic metal species from the electrode contribute with similar prominence as well as molecular bands from diatomic carbon. Finally, a comparison is provided of the results of these studies to other spectroscopic investigations of vacuum flashover from the literature.

Dicationic Acridinium/Carbene Hybrids as Strongly Oxidizing Photocatalysts.

A new design concept for organic, strongly oxidizing photocatalysts is described based upon dicationic acridinium/carbene hybrids. A highly modular synthesis of such hybrids is presented, and the dications are utilized as novel, tailor-made photoredox catalysts in the direct oxidative C-N coupling. Under optimized conditions, benzene and even electron-deficient arenes can be oxidized and coupled with a range of N-heterocycles in high to excellent yields with a single low-energy photon per catalytic turnover, while commonly used acridinium photocatalysts are not able to perform the challenging oxidation step. In contrast to traditional photocatalysts, the hybrid photocatalysts reported here feature a reversible two-electron redox system with regular or inverted redox potentials for the two-electron transfer. The different oxidation states could be isolated and structurally characterized supported by NMR, EPR, and X-ray analysis. Mechanistic experiments employing time-resolved emission and transient absorption spectroscopy unambiguously reveal the outstanding excited-state potential of our best-performing catalyst (+2.5 V vs SCE), and they provide evidence for mechanistic key steps and intermediates.

Superstructures of copper nanoclusters as NIR TADF emitters: solvent-dependent optical and morphological modulation.

Herein, we report 2-mercaptopyridine-templated copper nanoclusters (CuNCs) which display near infra-red (NIR) emission, both in the solid and colloidal states. Interestingly, the NIR emission can be modulated to orange emission by preparing the CuNCs in a mixed solvent system of chloroform and methanol instead of water. The drastic change in the photo-physical properties of the CuNCs when prepared in two different solvent systems is accompanied by a unique morphological tuning. Further studies reveal that the strong NIR emission is the result of thermally activated delayed fluorescence (TADF) which is confirmed by the long excited state lifetime (∼4 μs at room temperature), time resolved emission spectroscopy (TRES) measurements, temperature-dependent photoluminescence studies, temperature-dependent lifetime studies, and excitation-transmittance dependent TRES intensity measurements. The CuNCs exhibit an exceptionally small singlet-triplet energy gap of 58.2 meV, indicating a highly efficient TADF in the system. Moreover, the solvent-dependent morphological tuning of the nanocluster superstructures rendering a drastic change in the photo-physical signatures is the consequence of different ΔE(S1-T1) values for the CuNCs in different solvent environments. Further findings corroborate that the electronic structure of the surface ligands can also help us to tune the ΔE(S1-T1) energy gap for these nanoclusters.