Emitting Triplet State Research Articles

Brightening triplet excitons enable high-performance white-light emission in organic small molecules via integrating n–π*/π–π* transitions

Luminescent materials that simultaneously embody bright singlet and triplet excitons hold great potential in optoelectronics, signage, and information encryption. However, achieving high-performance white-light emission is severely hampered by their inherent unbalanced contribution of fluorescence and phosphorescence. Herein, we address this challenge by pressure treatment engineering via the hydrogen bonding cooperativity effect to realize the mixture of n–π*/π–π* transitions, where the triplet state emission was boosted from 7% to 40% in isophthalic acid (IPA). A superior white-light emission based on hybrid fluorescence and phosphorescence was harvested in pressure-treated IPA, and the photoluminescence quantum yield was increased to 75% from the initial 19% (blue-light emission). In-situ high-pressure IR spectra, X-ray diffraction, and neutron diffraction reveal continuous strengthening of the hydrogen bonds with the increase of pressure. Furthermore, this enhanced hydrogen bond is retained down to the ambient conditions after pressure treatment, awarding the targeted IPA efficient intersystem crossing for balanced singlet/triplet excitons population and resulting in efficient white-light emission. This work not only proposes a route for brightening triplet states in organic small molecules, but also regulates the ratio of singlet and triplet excitons to construct high-performance white-light emission.

Predicting Nonradiative Decay Rate Constants of Cyclometalated Ir(III) Complexes.

The theoretical calculation of the temperature-dependent nonradiative decay rate constant is fundamental for predicting the usefulness of transition-metal complexes for technological applications. Such a computation implies the determination of the barriers separating the emitting triplet state from metal-centered states, which are key mediators of this type of radiationless relaxation. We here do so for the two green-emitting cyclometalated Ir(III) complexes, [Ir(ppy)2(pyim)]+ and [Ir(diFppy)2(dtb-bpy)]+, of general formula [Ir(C∧N)2(N∧N)]+, performing DFT calculations with both B3LYP and PBE0 functionals. On the basis of the obtained results and the comparison with the experimental nonradiative decay rate constants, we conclude that B3LYP provides too low energy barriers to the metal-centered states, while the PBE0 provides reasonable values. We consequently recommend to avoid the use of the commonly employed B3LYP functional for the evaluation of such an energy barrier for cyclometalated Ir(III) complexes.

Simultaneous Thermally Stimulated Delayed Phosphorescence (TSDP) and Thermally Activated Delayed Fluorescence (TADF) in a Two-Coordinated Au(I) Bimetallic Complex Featuring a Tandem Carbene Structure.

A bimetallic, two-coordinated carbene-metal-amine (cMa) Au(I) complex featuring a twisted tandem carbene structure (NHC1-Au-NHC2-Au-carbazolyl) was synthesized. The molecular structure in single crystals revealed a large dihedral angle between the two carbene ligands, while the bridged carbene NHC2 and carbazolyl (Cz) ligands were coplanar. A bluish green thermally stimulated delayed phosphorescence (TSDP) was observed in crystals with an emission lifetime over 70 μs, which can be attributed to the spin allowed diabatic population of a high-lying emissive triplet state from the 3LE characterized low-lying ones. The small rotation energy barrier of Cz along the coordination bond allowed conformers with large dihedral angles between NHC2 and Cz. The ICT characterized S1 state was consequently stabilized to achieve a thermally accessible energy gap to facilitate ISC between triplets and the S1, leading to the thermally activated delayed fluorescence (TADF). Simultaneous TSDP and TADF dual emission can be recorded in its doped polymer film owing to the coexistence of these different conformers.

Spectrally Tunable Lead-Free Perovskite Rb2ZrCl6:Te for Information Encryption and X-ray Imaging.

A series of lead-free Rb2ZrCl6:xTe4+ (x = 0%, 0.1%, 0.5%, 1.0%, 2.0%, 3.0%, 5.0%, 10.0%) perovskite materials were synthesized through a hydrothermal method in this work. The substitution of Te4+ for Zr in Rb2ZrCl6 was investigated to examine the effect of Te4+ doping on the spectral properties of Rb2ZrCl6 and its potential applications. The incorporation of Te4+ induced yellow emission of triplet self-trapped emission (STE). Different luminescence wavelengths were regulated by Te4+ concentration and excitation wavelength, and under a low concentration of Te4+ doping (x ≤ 0.1%), different types of host STE emission and Te4+ triplet state emission could be achieved through various excitation energies. These luminescent properties made it suitable for applications in information encryption. When Te4+ was doped at high concentrations (x ≥ 1%), yellow triplet state emission of Te4+ predominated, resulting in intense yellow emission, which stemmed from strong exciton binding energy and intense electron-phonon coupling. In addition, a Rb2ZrCl6:2%Te4+@RTV scintillating film was fabricated and a spatial resolution of 3.7 lp/mm was achieved, demonstrating the potential applications of Rb2ZrCl6:xTe4+ in nondestructive detection and bioimaging.

Recent strategies for triplet-state emission regulation toward non-lead organic-inorganic metal halides.

Organic-inorganic metal halides (OIMHs) have strengthened the development of triplet-state emission materials due to their excellent luminescence performance. Due to the inherent toxicity of lead (Pb) significantly limiting its further advancement, numerous studies have been conducted to regulate triplet-state emission of non-Pb OIMHs, and several feasible strategies have been proposed. However, most of the non-Pb OIMHs reported have a relatively short lifetime or a low luminescence efficiency, not in favor of their application. In this review, we provide a summary of recent reports on the regulation of triplet-state emissions in non-Pb OIMHs to provide benefits for the design of innovative luminescent materials. Our focus is primarily on exploring the internal and external factors that influence the triplet-state emission. Starting from the luminescence mechanism, the current strategies for regulating triplet-state emissions are summarized. Moreover, by manipulating these strategies, it becomes feasible to achieve triplet-state emissions that span a range of colors from blue to red, and even extend into the near-infrared spectrum with high luminescence efficiency, while also increasing their lifetimes. This review not only provides fresh insights into the advancement of triplet-state emissions in OIMHs but also integrates experimental and theoretical perspectives to illuminate the trajectory of future research endeavors.

The Effect of Monodentate Co-Ligands on the Properties of Pt(II) Complexes Bearing a Tridentate C^N*N-Luminophore

In this study, the insertion of different monodentate co-ligands on Pt(II) complexes bearing a monoanionic C^N*N luminophore as a tridentate chelator was achieved beyond the previously reported chlorido- ([PtCl(L)]) and cyanido-decorated ([PtCN(L)]) analogues. To investigate the impact of the auxiliary ligand on the photophysical properties, we introduced a neutral carbonyl-ligand and observed a lower photoluminescence quantum yield (ΦL) than with a cyanido moiety. However, the direct substitution of the chlorido co-ligand by a NO-related derivative was not successful. Interestingly, the attempted reduction of the successfully inserted nitrito-N-ligand in [PtNO2(L)] resulted in the oxidation of the Pt(II)-center to Pt(IV), as demonstrated by X-ray diffractometry. For comparison, the trifluoroacetato Pt(II) and chlorido Pt(IV) complexes ([PtTFA(L)] and [PtCl3(L)], respectively) were also synthesized. The photophysical characterization revealed similar photoluminescence profiles for all complexes, indicating a weak effect of the co-ligand on the excited state; in fact, all complexes display emission from metal-perturbed ligand-centered states (even the Pt(IV) species). Nonetheless, longer excited state lifetimes (τav) suggest a reduced thermally-activated radiationless deactivation via metal-centered states upon exchange of the chlorido units for other monodentate entities, yet without significantly improving the overall ΦL at room temperature. The irreversible oxidation waves (measured via cyclic voltammetry) mostly stem from the Pt(II)-center; the co-ligand-related drop of these potentials correlates with the increasing σ-donating capacities of the ancillary ligand. In summary, an enhanced π-acceptor capacity does not necessarily improve the ΦL and can even impair radiative rates by compromising the perturbative participation of the metal center on the emissive triplet state; in addition, strong σ-donor abilities improve the phosphorescence efficiencies by hampering the thermal population of dissociative electronic configurations related to the participation of antibonding d*-orbitals at the metal center.

Room Temperature Phosphorescence in Chiral 0D Zn(II) Metal Halide Crystals for Multiple Anti‐Counterfeiting

AbstractThe development of metal halides that enable multiple information storage and cryptographic security is highly desirable but remains a challenge. Here, a pair of 0D Zn(II) metal halide enantiomers ZnCl2·R/S‐2‐MP with excitation wavelength‐dependent emission and room temperature phosphorescence properties are reported. Organic ligands via N─H···Cl hydrogen bonding induce structural chirality. In order to stabilize the triplet state exciton and achieve excellent photophysical properties, the organic ligands combine with halogens to promote emission. The differences between the photophysical properties of ZnCl2·R‐2‐MP and ZnCl2·S‐2‐MP are analyzed in depth. Furthermore, combined with femtosecond transient absorption (fs‐TA) results, the long phosphorescence lifetimes may originate from the triplet state emission due to the synergistic effect between the organic components and the inorganic metal halides. The design strategy of advanced multiple anticounterfeiting technology is further extended.

Spin Catalysis in Photochemical Reactions and Its Applications to Quantum Information Nanotechnology

Chemistry as a science about spin and electric charge of micro particles which provide driving forces of atomic interactions and molecular structure transformations fits pretty well to the modern Quantum Information Science (QIS) requirements. Today’s computers operate only electric current signals in the semiconductor networks but the electron-spin properties are not exploited in a large extend. Spintronics provides spin-polarized currents and manipulates magnetic spin interactions; it uses mostly solid state chemistry of heavy elements. But a rich organic chemistry of solvents and fin films offers a great potential for molecular electronics and quantum computing. Photo-excited organic complexes of the “chromophore–radical” type provide good promise for many technological applications in molecular spintronics and electronics, including QIS technology. The doublet state photo excitation of stable organic radical being delocalized onto the linked anthracene molecule within picoseconds and subsequently evolved into a quartet state for big radicals (a pure high spin state) of the mixed radical-triplet character presents a sensible spin-optical interface for qubit in quantum computing. This high-spin state is coherently addressable with EPR microwaves even at room temperature, with the optical read-out induced by intersystem crossing (ISC) to emissive triplet state. Such integration of radical luminescence and high-spin states EPR provides the organic materials involvement into emerging QIS technologies

Synergetic Conformational Regulations in Ground and Excited States for Realizing Stimulus-Responsive and Wide-Tuning Room-Temperature Phosphorescence.

Understanding the changes of molecular conformations is crucial for realizing multiple emissive triplet states in room-temperature phosphorescence (RTP) materials. In this work, we report two molecules, 4,4'-dimethylbenzil (DMBZ) and 4,4'-di-tert-butylbenzil (DBBZ) with conformation-dependent luminescence, and demonstrate that stimulus-responsive and wide-tuning RTP emissions can be realized via synergetic conformational regulations in ground and excited states. Due to conformational changes, DMBZ and DBBZ show abundant RTP variations upon external stimuli, including light, force, heat, and fumigation. Notably, DBBZ exhibits multiple conformational changes in both ground and excited states, which endow DBBZ with multiple emissive states and unique stimulus-responsive behaviors. DBBZ presents multiple phase transitions between the supercooled liquid state and different solid states accompanied by different phosphorescence transitions, in which the excited-state conformations are effectively regulated. Moreover, wide-range RTP regulations (between cyan, green, and yellow) are realized in both single component and host-guest systems of DBBZ, showing potential applications in temperature sensing, multicolor dynamic displays, and information encryption. These results may provide new visions for understanding the complicated conformational changes in the aggregated state, as well as unique insights into the relationship between molecular conformations, RTP emissions, and stimulus responsiveness.

Investigation of the N^C Ligand Effects on Emission Characteristics in a Series of Bis-Metalated [Ir(N^C)2(N^N)]+ Complexes.

A series of bis-metalated phosphorescent [(N^C)2Ir(bipyridine)]+ complexes with systematic variations in the structure and electronic characteristics of the N^C ligands were synthesized and characterized by using elemental analysis, mass spectrometry, NMR spectroscopy and X-ray crystallography. Investigation of the complexes' spectroscopic properties together with DFT and TD DFT calculations revealed that metal-to-ligand charge transfer (MLCT) and intraligand (LC) transition play key roles in the generation of emissive triplet states. According to the results of theoretical studies, the 3LC excited state is more accurate to consider as an intraligand charge transfer process (ILCT) between N- and C-coordinated moieties of the N^C chelate. This hypothesis is completely in line with the trends observed in the experimental absorption and emission spectra, which display systematic bathochromic shifts upon insertion of electron-withdrawing substituents into the N-coordinated fragment. An analogous shift is induced by expansion of the aromatic system of the C-coordinated fragment and insertion of polarizable sulfur atoms into the aromatic rings. These experimental and theoretical findings extend the knowledge of the nature of photophysical processes in complexes of this type and provide useful instruments for fine-tuning of their emissive characteristics.

Ultralong Near Infrared Room Temperature Phosphorescence in Cu(I) Metal‐Organic Framework Based‐on D–π–A–π–D Linkers

AbstractMaterials taking abundant advantage of triplet states luminescence have risen lots of attention in decades. In this work, a Cu(I) metal‐organic framework (MOF) with synchronous metal‐to‐ligand charge transfer (MLCT) state and triplet emission of the ligand is synthesized from a D–π–A–π–D ligand with suitable energy gap. The Cu(I) MOF possessed MLCT emission in the range of 450–505 nm with microsecond lifetimes (1.07 to 5.38 µs) and a triplet state emission in near infrared (NIR) region ≈705 nm with lifetimes of 1.85 ms at 300 K and 25.16 ms at 77 K, much longer than those of reported Cu(I) MOFs. Moreover, a white light is obtained through adjusting the relative intensity of dual peaks. More importantly, NIR long persistent luminescence of Cu‐MOF is observed by naked eyes under cryogenic condition. Multiple factors such as the delicate design of the D–π–A–π–D structure of ligand, the enhanced spin‐orbital coupling by Cu(I) networks, and the tight packing mode of the framework promote the generation of MLCT emission and ultralong NIR room temperature phosphorescence. The combination of calculation and experiment to analyse the luminescence mechanism of Cu(I) MOFs provides ideas for the development of Cu(I)‐based intelligently responsive materials with RTP properties.

Efficient blue-phosphorescent trans-bis(acyclic diaminocarbene) platinum(ii) acetylide complexes.

The lack of efficient and robust deep-blue phosphorescent metal complexes remains a significant challenge in the context of electroluminescent color displays. The emissive triplet states of blue phosphors are deactivated by low-lying metal-centered (3MC) states, which can be ameliorated by increasing the σ-donating ability of the supporting ligands. Here we unveil a synthetic strategy to access blue-phosphorescent complexes with two supporting acyclic diaminocarbenes (ADCs), known to be even stronger σ-donors than N-heterocyclic carbenes (NHCs). This new class of platinum complexes has excellent photoluminescence quantum yields, with four of six complexes affording deep-blue emission. Experimental and computational analyses are consistent with a pronounced destabilization of the 3MC states by the ADCs.

Energy Transfer Processes in the Excited States of an {[Ir(N C)2(N N)]+‐Rhodamine} Dyad: An Experimental and Theoretical Study

AbstractHerein we report the synthesis, characterization, photophysical and theoretical study of the luminescent dyad Ir‐RhB containing two emissive centers: The first fluorescent (RhB=rhodamine B) and the second phosphorescent (Ir=orthometalated iridium complex), bound with an aliphatic bridge. These nearly independent chromophores have triplet excited states which are very close in terms of energy, allowing for reversible energy transfer between them. The observed transient absorption spectra and their time dependent variations were interpreted in terms of a relatively simple kinetic model, where selective excitation of the iridium‐based chromophore affords the corresponding emissive triplet state, followed by its equilibration with the rhodamine based triplet state and simultaneous emissive relaxation to the dyad ground state. This model allows for analytical solution to give key characteristics of the dyad excited‐state dynamics, including the energy gap between these triplets (ΔE=0.017 eV) and the rate constant of energy transfer (k(Ir‐RhB)=6.0 ⋅ 108 s−1). These data were also verified by quantum chemical DFT and TD‐DFT calculations.

Theoretical insights into room temperature phosphorescence emission with anti-Kasha behavior in aggregate

Organic room temperature phosphorescence (RTP) materials with long lifetimes have shown promising applications in organic light emitting diodes and bioimaging fields. However, the inner luminescent mechanisms for RTP especially for high lying triplet state emission, have not been unveiled. Herein, based on density functional theory (DFT) and time-dependent density functional theory (TD-DFT), the photophysical properties of four RTP systems with triphenylethylene derivatives as skeletons are studied. Excited state dynamic process in aggregate is systematically studied by combining quantum mechanics with molecular mechanics (QM/MM) method coupled with thermal vibration correlation function (TVCF) method. Moreover, the intermolecular interactions are measured by the independent gradient model based on Hirshfeld partition (IGMH) method, the Huang-Rhys factor, reorganization energy and spin-orbit coupling (SOC) constant are calculated, radiative and non-radiative decay as well as intersystem crossing (ISC) and reverse intersystem crossing (RISC) processes are all investigated. Results indicate that the radiative decay process from the lowest triplet excited state (T1) to ground state (S0) is low and the non-radiative decay process is high, various calculations are also performed to exclude the emission process from T1 to S0, thus non-luminescence is determined for T1. Furthermore, a large energy gap between T2 and T1 is observed, and high radiative decay and low non-radiative decay processes from T2 to S0 are confirmed. Thus, the mechanisms of RTP from high lying triplet state T2 are revealed. Furthermore, through wise molecular design and detailed calculations, the mechanical insights are detected that the RTP emissions with anti-Kasha behavior are largely related to the unique molecular configurations with triphenylethylene derivatives as skeletons. Our studies give reasonable explanations for the previous experimental measurements and provide underlying perspectives for RTP mechanisms from high lying triplet state T2, which could promote the development of new efficient RTP emitters.

Generation of multiple triplet states in an orthogonal bodipy dimer: a breakthrough spectroscopic and theoretical approach.

Generation of triplet states in assemblies of organic chromophores is extremely appealing for their potential use in optoelectronic applications. In this work, we investigate the intricacies of triplet state generation in an orthogonal BODIPY dimer by combining delayed photoemission techniques with electronic structure calculations. Our analysis provides a deep understanding of the electronic states involved, and describes different competing deactivation channels beyond prompt radiative decay. In particular, we identify charge-transfer (CT) mediated intersystem crossing (ISC) as the most likely mechanism for the triplet state generation in this system. The different emission bands at long times can be associated with delayed fluorescence, CT emission and phosphorescence from multiple low-energy triplets. Interestingly, the dependence of the yield of triplet state population and emission profiles with the solvent polarity evidences the decisive role of the CT configuration in the fate of the photoactivated dimer, controlling the relative ISC, reverse ISC, and internal conversion efficiencies. Overall, the present results provide a rather complete description of the delayed photophysics in the BODIPY dimer, but are not able to fully rationalize the unexpected photoluminescence recorded at long wavelengths (≥ 900 nm). We hypothesize that the origin of this emission, not present in BODIPY monomers, emerges from intermonomer interactions triggered by intramolecular distortions opening up a new vision in the controverted mechanism driving the photophysical behavior from orthogonally linked organic monomers.

Mean-Field Effects on the Phosphorescence of Dinuclear Re(I) Complex Polymorphs.

A computational study rationalizes the different phosphorescence colors of two highly emitting crystal polymorphs of a dinuclear Re(I) complex, [Re2(μ-Cl)2(CO)6(μ-4,5-(Me3Si)2pyridazine)]. The electrostatic interactions between the charge distributions on neighboring molecules inside the crystal are responsible for the different stabilization of the emitting triplet state because of the different molecular packing. These self-consistent effects play a major role in the phosphorescence of crystals made of polar and polarizable molecular units, offering a powerful handle to tune the luminescence wavelength in the solid state through supramolecular engineering.

Brightly Luminescent Platinum Complexes of N∧C-∧N Ligands Forming Six-Membered Chelate Rings: Offsetting Deleterious Ring Size Effects Using Site-Selective Benzannulation.

Brightly emissive platinum(II) complexes (λemission,max = 607-612 nm) of the type RLPtCl are reported, where RL is a cyclometalated N∧C-∧N-coordinating ligand derived from 1,3-di(2-trifluoromethyl-4-phenanthridinyl)benzene (CF3LH) or 1,3-di(2-tert-butyl-4-phenanthridinyl)benzene (tBuLH). Metathesis of the chlorido ligand can be achieved under mild conditions, enabling isolation of ionic compounds with the formula [CF3LPtL']PF6 where L' = pyridine or (4-dimethylamino)pyridine (DMAP), as well as the charge-neutral species tBuLPt(C≡C─C6H4─tBu) (C≡C─C6H4─tBu = 4-tert-butylphenylacetylido). Compared with N∧N∧N-ligated Pt(II) complexes that form 5-membered chelates, these compounds all contain 6-membered rings. Expanding the chelate ring size from 5 to 6 has been previously demonstrated to enhance emission in some N∧N∧N-coordinated Pt(II) species─for example, in complexes of 2,6-di(8-quinolinyl)pyridine vs those of 2,2':6',2″-terpyridine─but in related N∧C-∧N-coordinated species, luminescence quantum yields are significantly lower for the 6-membered chelate ring complexes. Here, we demonstrate that site-selective benzannulation of the quinolinyl side-arms can offset the deleterious effect of changing the chelate ring-size and boost photophysical properties such as the quantum yield. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations suggest that benzannulation counterintuitively destabilizes the emissive triplet states compared to the smaller π-system, with the "imine-bridged biphenyl" form of the phenanthridinyl arm helping to buffer against larger molecular distortions, enhancing photoluminescence quantum yields up to 0.09 ± 0.02. The spontaneous formation under aerated conditions of a Pt(IV) derivative (CF3LPtCl3) is also reported, together with its molecular structure in the solid state.

Reduced Intrinsic Non-Radiative Losses Allow Room-Temperature Triplet Emission from Purely Organic Emitters.

Persistent luminescence from triplet excitons in organic molecules is rare, as fast non-radiative deactivation typically dominates over radiative transitions. This work demonstrates that the substitution of a hydrogen atom in a derivative of phenanthroimidazole with an N-phenyl ring can substantially stabilize the excited state. This stabilization converts an organic material without phosphorescence emission into a molecular system exhibiting efficient and ultralong afterglow phosphorescence at room temperature. Results from systematic photophysical investigations, kinetic modeling, excited-state dynamic modeling, and single-crystal structure analysis identify that the long-lived triplets originate from a reduction of intrinsic non-radiative molecular relaxations. Further modification of the N-phenyl ring with halogen atoms affects the afterglow lifetime and quantum yield. As a proof-of-concept, an anticounterfeiting device is demonstrated with a time-dependent Morse code feature for data encryption based on these emitters. A fundamental design principle is outlined to achieve long-lived and emissive triplet states by suppressing intrinsic non-radiative relaxations in the form of molecular vibrations or rotations.

NIR-Emissive Chromium(0), Molybdenum(0), and Tungsten(0) Complexes in the Solid State at Room Temperature.

The development of NIR emitters based on earth‐abundant elements is an important goal in contemporary science. We present here Cr(0), Mo(0), and W(0) carbonyl complexes with a pyridyl‐mesoionic carbene (MIC) based ligand. A detailed photophysical investigation shows that all the complexes exhibit dual emissions in the VIS and in the NIR region. The emissive excited states are assigned to two distinct triplet states by time‐resolved emission and step‐scan FTIR spectroscopy at variable temperature, supported by density functional theory. In particular, the NIR emissive triplet state exhibits unprecedented lifetimes of up to 600±10 ns and quantum yields reaching 1.7 ⋅ 10−4 at room temperature. These are the first examples of Cr(0), Mo(0) and W(0) complexes that emit in the NIR II region.

Pyridine-Conjugated Pillar[5]arene: From Molecular Crystals of Blue Luminescence to Red-Emissive Coordination Nanocrystals.

A luminescent molecular crystal (P5bipy) and a Cu(I)-coordinated luminescent nanocrystal (Cu(I)-P5bipy) have been prepared concurrently using one conjugated pillar[5]arene macrocycle via a facile supramolecular self-assembling strategy. The molecular crystal shows enhanced luminescence compared with unmodified pillar[5]arene, attributed to its conjugated structure and staggered packing mode, while the coordination nanocrystal exhibits well-defined crystalline structures and long-lifetime triplet state emission along with pronounced solvochromic features.