Triplet Emission Research Articles

Stable Long-Persistent Luminescence from Self-Activated CaSb2O6 Induced by Intrinsic Defects.

Long-persistent luminescence (LPL) materials have attracted intensive attention due to their fascinating emission after excitation. However, current LPL materials typically depend on external doping to introduce traps or emitting centers, resulting in a complex synthesis and controllability. For the first time, we develop another category of undoped LPL materials based on antimonate CaSb2O6, which exhibits blue LPL for over 8000 s. Both experimental and theoretical evidence indicate that excitons are trapped by intrinsic oxygen vacancies. Then, they are detrapped and recombine through singlet and triplet emission of Sb3+ to form LPL. Moreover, CaSb2O6 maintains approximately 100% of its initial LPL performance and structural integrity even after being treated under 1000 °C, UV irradiation, and extreme conditions (pH = 1 or 13). This study highlights the significant potential of antimonates as robust and versatile luminescent materials.

Origin of Ca II emission around polluted white dwarfs

Dozens of white dwarfs with anomalous metal polluted atmospheres are currently known to host dust and gas discs. The line profiles of the Ca II triplet emitted by the gas discs show a significant asymmetry. In recent decades, researchers have also discovered several minor planets orbiting such white dwarf stars. The most challenging burden of modelling gas discs around metal polluted white dwarfs is to simultaneously explain the asymmetry and metal pollution of the star's atmosphere over a certain period of time. Furthermore, models should also be consistent with other aspects of the observations, such as the morphology of the emission lines. This paper aims to construct a self-consistent model to explain the simultaneous white dwarf pollution and Ca II line asymmetry over at least three years. In our model, an asteroid disintegrates in an eccentric orbit, periodically entering below the star's Roche limit. The debris resulting from the disintegration sublimates at a temperature of 1500 K, producing gas that viscously spreads to form a disc. The evolution of the disc is studied over a period of 1.2 years (over 21000 orbits) using two-dimensional hydrodynamic simulations. Synthetic Ca II line profiles are calculated using the surface mass density and velocity distributions provided by the simulations, taking into account for the first time the asymmetric velocity distribution in the disc. An asteroid disintegrating on an eccentric orbit gives rise to the formation of an asymmetric disc and asymmetric Ca II triplet emission. Our model can explain the periodic reversal of the redshifted and blueshifted peak of the Ca II lines caused by the precession of the disc on timescales of 10.6 to 177.4 days. Our work suggests that the persistence of Ca II asymmetry over decades and its periodic change in the peaks can be explained by asteroids on eccentric orbits in two scenarios. In the first case, the asteroid disrupts on a short timescale (a couple of orbits), and the gas has a low viscosity range ($0.001< to maintain the Ca II signal for decades. In the other scenario, the asteroid disrupts on a timescale of a year, and the viscosity of the gas is required to be high, $

Anomalous Pressure‐Induced Blue‐Shifted Emission of Ionic Copper‐Iodine Clusters: The Competitive Effect between Cuprophilic Interactions and Through‐Space Interactions

AbstractDeveloping ionic copper‐iodine clusters with multiple emitting is crucial for enriching lighting and display materials with various colors. However, the luminescent properties of traditional ionic copper‐iodine clusters are often closely associated with low‐energy cluster‐centered triplet emission, which will redshift further as the Cu⋅⋅⋅Cu bond length decreases. This article utilizes a pressure‐treated strategy to achieve an anomalous pressure‐induced blue‐shifted luminescence phenomenon in ionic Cu4I6(4‐dimethylamino‐1‐ethylpyridinium)2 crystals for the first time, which is based on dominant through‐space charge‐transfer (TSCT). Herein, we reveal that the more advantageous through‐space interactions in the competition between cuprophilic interactions and through‐space interactions can lead to a blue‐shifted luminescence. High‐pressure angle‐dispersive X‐ray diffraction and high‐pressure infrared experiments show that the enhanced through‐space interactions mainly originate from forming new intermolecular C−H⋅⋅⋅I hydrogen bonds and the enhancement of van der Waals interactions between organic cations and anionic clusters. Theoretical calculations and experimental studies of excited‐state dynamics confirm that the blue‐shifted emission is due to the increased energy gap between the excited triplet and ground states caused by the electron delocalization under stronger through‐space interactions. This work deepens previous understanding and provides a new avenue to design and synthetic ionic copper‐iodine clusters with high‐energy TSCT emission.

Anomalous Pressure-Induced Blue-Shifted Emission of Ionic Copper-Iodine Clusters: The Competitive Effect between Cuprophilic Interactions and Through-Space Interactions.

Developing ionic copper-iodine clusters with multiple emitting is crucial for enriching lighting and display materials with various colors. However, the luminescent properties of traditional ionic copper-iodine clusters are often closely associated with low-energy cluster-centered triplet emission, which will redshift further as the Cu⋅⋅⋅Cu bond length decreases. This article utilizes a pressure-treated strategy to achieve an anomalous pressure-induced blue-shifted luminescence phenomenon in ionic Cu4I6(4-dimethylamino-1-ethylpyridinium)2 crystals for the first time, which is based on dominant through-space charge-transfer (TSCT). Herein, we reveal that the more advantageous through-space interactions in the competition between cuprophilic interactions and through-space interactions can lead to a blue-shifted luminescence. High-pressure angle-dispersive X-ray diffraction and high-pressure infrared experiments show that the enhanced through-space interactions mainly originate from forming new intermolecular C-H⋅⋅⋅I hydrogen bonds and the enhancement of van der Waals interactions between organic cations and anionic clusters. Theoretical calculations and experimental studies of excited-state dynamics confirm that the blue-shifted emission is due to the increased energy gap between the excited triplet and ground states caused by the electron delocalization under stronger through-space interactions. This work deepens previous understanding and provides a new avenue to design and synthetic ionic copper-iodine clusters with high-energy TSCT emission.

Influences of hydrogen-bond promoting hydroxyl group on photophysical and catalytic properties of lanthanide pyridine dicarboxylate frameworks

To study the influences of hydrogen bonding interactions on photophysical properties and catalytic activities with insignificant interference from structural disparity, two new isostructural [LnIII2(OH-pda)(ox)2(H2O)4]∙4H2O coordination polymers (LnIII = EuIII (I) and NdIII (IIa), OH–H2pda = 4-hydroxypyridine-2,6-dicarboxylic acid, H2ox = oxalic acid) were synthesized and characterized. They are also isostructural to [NdIII2(pda)(ox)2(H2O)4]∙4H2O (IIb), H2pda = pyridine-2,6-dicarboxylic acid) containing pda2− instead of OH-pda2-. The identical framework structure of IIa and IIb with additional hydrogen bonding interactions in IIa due to –OH group of OH-pda2- has been presented. Based on IIa and IIb, the effects of the –OH group on photophysical properties and catalytic activities were then investigated without structural bias. With reference to the UV–vis absorption and phosphorescent emission spectroscopy, the singlet (S1) and triplet (T1) state energies of OH–H2pda (41,600 and 19,200 cm−1), H2pda (48,200 and 23,300 cm−1), OH-pda2- (IIa, 41,400 and 22,500 cm−1) and pda2− (IIb, 47,100 and 23,300 cm−1) were determined from which the influences of the –OH group have been revealed. Important roles of the –OH group as electron-donating group as well as hydrogen bond promoter have been proposed. Catalytic activities of IIa and IIb were comparatively examined using the solvent-free CO2 cycloaddition reaction at atmospheric pressure with epichlorohydrin in the presence of tetrabutylammonium bromide. The inferior performance of IIa (maximum yield of 62(±2)%) to IIb (maximum yield of 68(±2)%) was unexpectedly disclosed and the drawback of the substantial involvement of the catalytic sites in hydrogen bonding interactions has been demonstrated. Their reusability was additionally explored.

Mono and binuclear Pt(II) complexes incorporated with NHC ligands: syntheses, photophysical properties, and acid vapor responses

Three mononuclear complexes (PtL1H, PtL2H, and PtL3H) and one binuclear complex (Pt2L1) have here been prepared using the bis-carbene ligand of 1,3-propylene-bis(1,3-dihydro-3-butyl-2H-imidazol-2-ylidene) and one of three rigid planar ligands of dibenzo[f,h]quinoxaline (L1H2), dibenzo[a,c]phenazine (L2H2), and tribenzo[a,c,i]phenazine (L3H2). These four complexes were fully characterized by nuclear magnetic resonance (NMR), high-resolution mass spectrometry (HRMS), and elemental analyses. Moreover, the two binuclear complexes Pt2L2 and Pt2L3 could not be isolated, but Pt2L3 was isolated and characterized by single-crystal X-ray diffraction (XRD). Complexes PtL1H, PtL2H, and Pt2L1 exhibited phosphorescence in N2-degassed dichloromethane (DCM) solution at 563 nm, 656 nm, and 624 nm, respectively. Also, Pt2L1 exhibited triplet emission at 553 nm in a 2 wt% PMMA film, with the highest Ф of 63 % and τ of 23.8 μs. Moreover, complexes PtL1H and Pt2L1 were deposited on quartz plates to monitor formic acid vapor and acetic acid vapor. The plates that were covered with PtL1H exhibited phosphorescent quenching in both formic acid and acetic acid. However, the plates that were covered with Pt2L1 did only show a prompt response to formic acid, but were not sensitive to acetic acid.

A Luminescent Hybrid Bimetallic Halide Family with Solvent‐Coordinated Rare Earth and Alkaline Earth Metals

AbstractHybrid metal halides are an extraordinary class of optoelectronic materials with extensive applications. To further diversify and study the in‐depth structure‐property relations, we report here a new family of 21 zero‐dimensional hybrid bimetallic chlorides with the general formula A(L)n[BClm] (A=rare earth (RE), alkaline earth metals and Mn; L=solvent ligand; and B=Sb, Bi and Te). The RE(DMSO)8[BCl6] (RE=La, Ce, Sm, Eu, Tb, and Dy; DMSO=dimethyl sulfoxide) series shows broadband emission attributed to triplet radiative recombination from Sb and Bi, incorporating the characteristic emission of RE metals, where Eu(DMSO)8[BiCl6] shows a staggering PL quantum yield of 94 %. The pseudo‐octahedral [SbCl5] with Cl vacancy in AII(DMSO)6[SbCl5] (AII=Mg, Ca and Mn) and the square pyramidal [SbCl5] in AII(TMSO)6[SbCl5] (TMSO=tetramethylene sulfoxide) enhance the stereoactive expression of the 5 s2 lone pairs of Sb3+, giving rise to the observation of dual‐band emission of singlet and triplet emission, respectively. A series of Te(IV) analogues have been characterized, showing blue‐light‐excitable single‐band emission. This work expands the materials space for hybrid bimetallic halides with an emphasis on harnessing the RE elements, and provides important insights into designing new emitters and regulating their properties.

A Luminescent Hybrid Bimetallic Halide Family with Solvent-Coordinated Rare Earth and Alkaline Earth Metals.

Hybrid metal halides are an extraordinary class of optoelectronic materials with extensive applications. To further diversify and study the in-depth structure-property relations, we report here a new family of 21 zero-dimensional hybrid bimetallic chlorides with the general formula A(L)n[BClm] (A=rare earth (RE), alkaline earth metals and Mn; L=solvent ligand; and B=Sb, Bi and Te). The RE(DMSO)8[BCl6] (RE=La, Ce, Sm, Eu, Tb, and Dy; DMSO=dimethyl sulfoxide) series shows broadband emission attributed to triplet radiative recombination from Sb and Bi, incorporating the characteristic emission of RE metals, where Eu(DMSO)8[BiCl6] shows a staggering PL quantum yield of 94 %. The pseudo-octahedral [SbCl5] with Cl vacancy in AII(DMSO)6[SbCl5] (AII=Mg, Ca and Mn) and the square pyramidal [SbCl5] in AII(TMSO)6[SbCl5] (TMSO=tetramethylene sulfoxide) enhance the stereoactive expression of the 5 s2 lone pairs of Sb3+, giving rise to the observation of dual-band emission of singlet and triplet emission, respectively. A series of Te(IV) analogues have been characterized, showing blue-light-excitable single-band emission. This work expands the materials space for hybrid bimetallic halides with an emphasis on harnessing the RE elements, and provides important insights into designing new emitters and regulating their properties.

Suppressing the Thermal Quenching Effect via a Cluster Conformer in Copper(I)-Iodide Coordination Polymeric Phosphors for High-Power White LED Lighting.

High-power LED lighting is a crucial challenge due to the notorious thermal quenching (TQ) effect of traditional phosphors at high operating currents, which would result in poor device performance and hamper practical optoelectronic application. Herein, we demonstrate ligand engineering of a cubane- versus staircase-like [Cu4I4] conformer as a node in coordination polymers, which remarkably suppresses the TQ effect of cluster-based photoluminescence. For complex 1 (the formula [Cu4I4(bbimb)2]n) with the cubane-like [Cu4I4] conformer as a node, the metallophilicity interaction enables ultrabright triplet emission with a photoluminescence quantum yield over 82%, and the phonon-assisted detrapping process of excitons effectively suppresses the TQ effect in the wide temperature range. In contrast, the staircase-like [Cu4I4] conformer as a node in complex 2 (the formula [Cu4I4(bbtmb)2]n) exhibits a serious TQ effect over the investigated temperature. Phosphor-converted white LEDs (pc-wLEDs) were fabricated by integrating the cluster-based coordination polymers as a color converter, and their electroluminescence performances were investigated under high bias currents. The prototype pc-wLED device by incorporating the phosphor with the suppressed TQ effect exhibits a continuous rise in brightness under a high bias current of 300 mA. The results demonstrate that ligand engineering of the cluster conformer via suppressing the TQ effect proves efficient in designing an ideal color converter for high-power pc-wLED lighting.

Cyclometalated Pt(II)C^N phosphors bearing a bis(diphenylphorothioyl) amide ligand: synthesis and photophysical properties

Six Pt(II) complexes bearing a primary phenylpyridine (ppy) ligand or a ppy derivative and two Pt(II) complexes bearing a primary 8-hydroxyquinoline (hqnl) or 7-bromo-8-quinolinol ligand have been prepared via coordination with an auxiliary bis(diphenylphosphothionyl) amide (HStpip) ligand. All eight complexes were characterized by NMR (1H,13C, and 31P), HRMS, and elemental analysis. In addition, complexes 2, 4, 5, and 8 were characterized by single crystal XRD. The eight complexes were not emissive in solution under N2 at room temperature (r.t.). However, they all exhibited an intense emission in the solid state and in 2 wt.% polymethyl methacrylate (PMMA) films. In particular, 5 bearing a primary 2-([1,1'-biphenyl]-3-yl)-4-phenylpyridine ligand exhibited a triplet emission at 525 and 552 nm with a quantum yield of 80% in pure solid state. Density functional theory (DFT) and time dependent (TD) DFT calculations were performed for optimization and predicting the excitation properties of 2, 4, 5, and 8. The computational results reveal that the intrinsic triplet emissions of 2, 4, and 5 are the result of combinations of ligand-to-metal charge transfer (LMCT) (π*(ppy) → d(Pt)) and ligand-to-ligand charge transfer (LLCT) (π*(ppy) → p(Stpip)), whereas the triplet emission of 8 shows a π*–π character with a small LMCT (π*(hqnl) → d(Pt)) component.

Double-Model Decay Strategy Integrating Persistent Photogenic Radicaloids with Dynamic Circularly Polarized Doublet Radiance and Triplet Afterglow.

Organic phosphors integrating circularly polarized persistent luminescence (CPPL) across the visible range are widespread for applications in optical information encryption, bioimaging, and 3D display, but the pursuit of color-tunable CPPL in single-component organics remains a formidable task. Herein, via in situ photoimplanting radical ion pairing into axial chiral crystals, we present and elucidate an unprecedented double-module decay strategy to achieve a colorful CPPL through a combination of stable triplet emission from neutral diphosphine and doublet radiance from photogenic radicals in an exclusive crystalline framework. Owing to the photoactivation-dependent doublet radiance component and an inherent triplet phosphorescence in the asymmetric environment, the CPL vision can be regulated by altering the photoactivation and observation time window, allowing colorful glow tuning from blue and orange to delayed green emission. Mechanism studies clearly reveal that this asymmetric electron migration environment and hybrid n-π* and π-π* instincts are responsible for the afterglow and radical radiance at ambient conditions. Moreover, we demonstrate the applications of colorful CPPL for displays and encryption via manipulation of both excitation and observation times.

Excited state dynamics of Bi3+ centers in cubic Gd2O3

Photoluminescence characteristics of Gd2O3:Bi are studied in the 4.2–800 K temperature range by the time-resolved spectroscopy methods. Purely cubic structure of Gd2O3:Bi is confirmed by XRD. The luminescence of Bi3+(S6) and Bi3+(C2) centers is found to arise from the electron transitions from the emitting level of the triplet excited state of Bi3+, corresponding to the 3P1 → 1S0 transitions of the free Bi3+ ion. Relaxation processes in the triplet excited state of Bi3+ ions do not result in the population of the lowest-energy metastable level. The absence of the radiative transitions, corresponding to the 3P0 → 1S0 transitions of the free Bi3+ ion, explains the short (0.3–2.0 μs) decay time of the triplet emission of Bi3+ even at 4.2 K. The conclusion is made that the fast luminescence decay cannot be caused by the mixing of the metastable and emitting levels of the triplet excited state of Bi3+ by the magnetic field created at the Bi3+ site by the magnetically ordered Gd3+ sublattice. The electron transfer and recombination processes, resulting in the appearance of the photo- and thermally stimulated electron recombination luminescence of Bi3+(S6) and Bi3+(C2) centers under excitation in the Eexc > 4.3 eV energy region, are also discussed. The energy level positions of the Bi3+(S6) and Bi3+(C2) centers in the band gap of Gd2O3 are estimated.

A cyclometalated Pt(II)-Pt(II) clamshell dimer with a triplet emission at 887 nm.

Here, a cyclometalated Pt(II) clamshell dimer (complex 2) has been synthesized with the primary ligand of dibenzo(f,h)quinoxaline and an ancillary ligand of N,N'-diphenylformamidine. In addition, a mononuclear Pt(II) complex 1a and a binuclear Pt(II) complex 1b were also prepared. Complex 1a was coordinated by one cyclometalated ligand of dibenzo(f,h)quinoxaline, one chloride ion, and one N,N'-diphenylformamidine. Complex 1b was coordinated by one cyclometalated ligand of dibenzo(f,h)quinoxaline, two chloride ions, and two N,N'-diphenylformamidines. All of these three complexes were characterized by nuclear magnetic resonance (NMR) spectroscopy, high-resolution mass spectrometry (HRMS), elemental analyses, and single-crystal X-ray diffraction (XRD). The Pt-Pt distance in complex 2 was 2.8439(2) Å. It also exhibited a near-infrared (near-IR) emission at 887 nm in the pure solid state. On the other hand, complexes 1a and 1b exhibited triplet emission at 589 and 660 nm, respectively, in the pure solid state. Furthermore, in 2 wt% poly(Me methacrylate) (PMMA) films, complex 1a showed a triplet emission at 548 nm (with Φ = 84% and τ = 5.53 μs) and complex 1b showed an emission at 627 nm (with Φ = 79% and τ = 4.07 μs). Due to its great photophysical properties, complex 1b was deposited onto quartz plates for the detection of organic solvent vapors and it showed unique emission quenching for the vapor of tetrahydrofuran.

Time-dependent room temperature phosphorescent colors from a sulfur-doped carbon dot-based composite for advanced information encryption and anti-counterfeiting applications

Sulfur doping regulates the bandgap of the carbon dots, and time-dependent afterglow color emission is realized in a carbon dot-based composite via the multiple triplet emissions with distinct lifetimes.

Thermal‐Annealing Enhanced Room‐Temperature Phosphorescence of Polymer‐Based Organic Materials

AbstractPolymer‐based organic room‐temperature phosphorescent (RTP) materials have recently attracted significant attention. In most of the previous works, ‘chemical approaches’ were applied to improve the performance of RTP materials, such as designing certain phosphors or selecting specific polymeric matrixes. However, enhancing triplet emission through facile ‘physical approaches’ is rarely reported. In this study, enhanced RTP emissions of phosphor‐doped polymers are reported by thermal annealing. By doping a difluoroboron β‐diketonate derivative into poly(diacetone acrylamide) (PDAAM), green RTP emissions can be obtained. After thermal annealing at 125 °C for 5 min, the afterglow duration of RTP increases from 2.6 to 5.3 s and also the brightness of RTP emission exhibits a threefold increase. Such post‐treatment is applicable for various polymeric matrixes. The mechanism underlying thermal‐annealing enhanced RTP is investigated. Moreover, it demonstrates that controlled RTP by thermal annealing can be used in information encryption and anti‐counterfeiting. This work provides new insight into the development of organic RTP materials with tunable emissions.

Alkynylphosphonium Pt(II) Complexes: Synthesis, Characterization, and Features of Photophysical Properties in Solution and in the Solid State.

A series of heteroleptic bis-alkynyl-diimine mononuclear Pt(II) complexes with alkynylphosphonium and di-tert-butyl-2,2'-bipyridine (dtbpy) ligands have been prepared and characterized by spectroscopic methods and single-crystal XRD. The Pt(II) complexes obtained in the present study demonstrate triplet emission in solution, which originates from 3MLCT/3LC states where the nature of the π-conjugated linker in the alkynylphosphonium ligand manages the contributions of each transition, and this conclusion is supported by DFT calculations. Additionally, the presence of the phosphonium group connected to alkynyl through the π-conjugated linker enhances nonlinear optical properties of the Pt(II) complexes increasing two-photon absorption cross section up to 400 GM. In the solid state, the Pt(II) complexes demonstrate emission that is attributed to 3MMLCT transitions due to the presence of Pt-Pt metallophilic interactions, and the reversible assembly and disassembly of these interactions by grinding and solvent treatment are responsible for the mechanochromic luminescence. It has been experimentally shown that stimuli-responsive emission of the Pt(II) complexes is the result of a "monomer/dimer" transformation; this conclusion is confirmed by DFT calculations for discrete complexes and different dimers with or without Pt-Pt interactions.

Polarity-Tunable Luminescence and Intersystem Crossing of a Zinc(II) Diimine Dithiolate Complex.

Combined density functional theory and multireference configuration interaction methods including spin-orbit interactions have been employed to investigate the photophysical properties and deactivation pathways of a zinc diimine dithiolate complex involving the phenanthroline derivative bathocuproine and the dianionic dithiosquarate as chelating ligands. Zn(batho)(dtsq) is one of the few luminescent zinc complexes for which triplet emission had been reported in the solid state [Gronlund, P. Inorg. Chim. Acta 1995, 234, 13-18]. Because of the high dipole moment of the complex in the electronic ground state, ligand-to-ligand charge-transfer (LLCT) states experience strong hypsochromic shifts in polar media, while ligand-centered (LC) states are nearly unaffected. Rate constants for the thermally activated upconversion of the TLLCT population to the SLLCT state are promising due to a small singlet-triplet energy gap and the participation of the sulfur in the electronic excitation, but the TLLCT state is not the lowest-lying excited triplet state in ethanol solution. In addition to the TLLCT electronic structure, TLC(batho)' and TLC(dtsq) ππ* excitations form minima on the T1 potential energy surface. The SLLCT luminescence is expected to be quenched at the nanosecond time scale by the dark TLC(dtsq)ππ* state. Moreover, a TLC(dtsq)σπ* state has been identified, which leads to degradation of the compound. In mildly polar media, the dark triplet LC states are energetically inaccessible and the lowest excited singlet and triplet states clearly exhibit an LLCT character. However, their mutual spin-orbit coupling is reduced to the extent that reverse intersystem crossing is not very likely at room temperature. While Zn(diimine)(dithiolate) complexes continue to be perceived as an interesting substance class with potential application as emitters in electroluminescent devices, the particular Zn(batho)(dtsq) complex is not considered suitable for that purpose.

Trap or Triplet? Excited-State Interactions in 2D Perovskite Colloids with Chromophoric Cations.

Movement of energy within light-harvesting assemblies is typically carried out with separately synthesized donor and acceptor species, which are then brought together to induce an interaction. Recently, two-dimensional (2D) lead halide perovskites have gained interest for their ability to accommodate and assemble chromophoric molecules within their lattice, creating hybrid organic-inorganic compositions. Using a combination of steady-state and time-resolved absorption and emission spectroscopy, we have now succeeded in establishing the competition between energy transfer and charge trapping in 2D halide perovskite colloids containing naphthalene-derived cations (i.e., NEA2PbX4, where NEA = naphthylethylamine). The presence of room-temperature triplet emission from the naphthalene moiety depends on the ratio of bromide to iodide in the lead halide sublattice (i.e., x in NEA2Pb(Br1-xIx)4), with only bromide-rich compositions showing sensitized emission. Photoluminescence lifetime measurements of the sensitized naphthalene reveal the formation of the naphthalene triplet excimer at room temperature. From transient absorption measurements, we find the rate constant of triplet energy transfer (kEnT) to be on the order of ∼109 s-1. At low temperatures (77 K) a new broad emission feature arising from trap states is observed in all samples ranging from pure bromide to pure iodide composition. These results reveal the interplay between sensitized triplet energy transfer and charge trapping in 2D lead halide perovskites, highlighting the need to carefully parse contributions from competing de-excitation pathways for optoelectronic applications.

Meteors May Masquerade as Lightning in the Atmosphere of Venus

AbstractLightning in the atmosphere of Venus is either ubiquitous, rare, or non‐existent, depending on how one interprets diverse observations. Quantifying when and where, or even if lightning occurs, would provide novel information about Venus' atmospheric dynamics and chemistry. Lightning is also a potential risk to future missions, which could float in the cloud layers (∼50–70 km above the surface) for up to an Earth‐year. Over decades, spacecraft and ground‐based telescopes have searched for lightning at Venus using many instruments, including magnetometers, radios, and optical cameras. Two optical surveys (from the Akatsuki orbiter and the 61‐inch telescope on Mt. Bigelow, Arizona) observed several flashes at 777 nm (the unresolved triplet emission lines of excited atomic oxygen) that have been attributed to lightning. This conclusion is based, in part, on the statistical unlikelihood of so many meteors producing such energetic flashes, based in turn on the presumption that a low fraction (<1%) of a meteor's optical energy is emitted at 777 nm. We use observations of terrestrial meteors and analogue experiments to show that a much higher conversion factor (∼5%–10%) should be expected. Therefore, we calculate that smaller, more numerous meteoroids could have caused the observed flashes. Lightning is likely too rare to pose a hazard to missions that pass through or dwell in the clouds of Venus. Likewise, small meteoroids burn up at altitudes of ∼100 km, roughly twice as high above the surface as the clouds, and also would not pose a hazard.

Amplified Triplet Emission of Organic Periphery Groups by Exothermic Triplet-Triplet Energy Transfer from the 3MLCT State of an Ir(pmi)3 Core Complex to the 3LC State of Geometrically Confined Carbazole/Naphthyl Tethers.

To investigate the excited-state properties of metal-organic bichromophores, including energy transfer mechanisms, a series of new homoleptic N-heterocyclic carbene (NHC)-based iridium(III) complexes were prepared by incorporating a peripheral naphthalene (Np) (Ir(Nppmi)3: fac-/mer-Ir(1-Nppmi)3 and fac-/mer-Ir(2-Nppmi)3) or carbazole (Cz) (Ir(Czpmi)3: fac-/mer-Ir(o-Czpmi)3, fac-/mer-Ir(m-Czpmi)3, and fac-/mer-Ir(p-Czpmi)3) unit to the phenyl moiety of the phenylimidazole (pmi) ligand. Through a series of photophysical analyses and femtosecond time-resolved absorption (fs-TA) spectroscopy, it was discovered that the phosphorescence of the Ir core, (Ir(pmi)3), was considerably quenched, while intense phosphorescence peaks arising from the excited triplet Np (3Np*)/Cz (3Cz*) species were primarily observed at room temperature (r.t.) and low temperature. Such amplified phosphorescence of the tethered organic Np and Cz units originated from triplet-triplet energy transfer (TTET) from the high-lying metal-to-ligand charge transfer (3MLCT) state of the Ir(pmi)3 core to the ligand-centered triplet state (3LC) of the peripheral Np and Cz units. This result indicates that the exothermic intramolecular energy transfer (IET) in the excited triplet state realizes the efficient phosphorescent emission of geometrically confined organic tethers.