Radiative Decay Processes Research Articles

Influence of Halogen Substituents on the Photophysical Properties of 7-Hydroxycoumarin: Insights from Experimental and Theoretical Studies.

Benzopyrone is a popular fluorescent scaffold, but how chemical modifications affect its properties is less understood. We investigated this using halogenated 7-hydroxycoumarin, unsubstituted 4-methylumbiliferone, and ortho-chloro and bromo substitutions on the phenolic ring. Experimental charge density data and computational methods revealed that halogenation at the ortho position significantly reduced quantum yield (QY). Specifically, 7-hydroxycoumarin (1) had a QY of 70%, while ortho-chloro (2) and ortho-bromo (3) had QYs of 61% and 30%, respectively. Experimental data showed that all probes excited similarly, but the electrostatic potential and dipole moments indicated that 2 and 3 dissipated excitation energy more easily due to charge separation. The heavy-atom effect of Cl and Br did not fully explain the QY reductions, suggesting other radiative decay processes were involved. By incorporating spin-orbit coupling (SOC) effects, we estimated intersystem crossing (ISC) and phosphorescence rates, providing theoretical QYs of 78% for 1, 59% for 2, and 15% for 3. The large deviation for 3 was attributed to its higher SOC potential. Our findings indicate that 3's reduced QY results from a mix of SOC-induced ISC and charge dissipation, while 2's reduction is primarily due to charge separation. Further studies are needed to validate this approach with other scaffolds.

Theoretical studies on the excited-state properties of di(pyridinyl)methanone-based emitters with efficient thermally activated delayed fluorescence

The excited-state properties of seven thermally activated delayed fluorescence (TADF) emitters with di(pyridinyl)methanone acceptor were investigated using DFT and TD-DFT methods. The results indicate that the species and number of donors strikingly impact the excited-state nature. The mono-substituted donor increases the local-excited singlet (1LE) and local-excited triplet (3LE) contribution, promoting the radiative decay processes and strengthening spin–orbit coupling (SOC) between S1 and T1 states. The decreased charge transfer (CT) contribution of S1 gives rise to a much smaller ΔEST, and the mixed CT-LE nature of T1 guarantees the strong SOC for the designed emitters 1–4 and 6, endowing them with high reverse intersystem crossing rates.

Host-guest interaction induced room-temperature phosphorescence enhancement of organic dyes: a computational study.

To achieve the effective regulation of organic room temperature phosphorescence (RTP) in supramolecular systems, the elucidation of host-guest interactions in RTP is of vital importance. Herein, we employed two organic dyes (PYCl and PYBr) and their four host-guest complexes with CB[6] and CB[7] and explored the mechanism of host-guest interaction induced RTP enhancement using quantum mechanics/molecular mechanics (QM/MM) approach. For the two organic dyes, we found that the better RTP performance of PYBr than PYCl is attributed to intersystem crossing (ISC) augmentation induced by the heavy atom effect. Binding to CB[6] through host-guest interactions can simultaneously accelerate the radiative decay process by increasing the transition dipole moment of T1 → S0 (μT1→S0), block the nonradiative decay process, and promote the ISC process, eventually leading to a remarkably boosted RTP. Upon complexation, the conversion of S1 from 1(n, π*) to 1(π, π*) is key to μT1→S0 enhancement; reduced reorganization energies reflect the suppression of the nonradiative decay process by restricting the rotation of rings A and B in organic dyes. In addition, the promoted ISC process is due to the activation of more ISC channels between S1 and high-lying triplet states with large spin-orbital coupling constants and small energy gap. The case of CB[7]-type complexes is much different, because of the extremely large cavity size of CB[7] for encapsulation. This work proposes the mechanism of host-guest interaction-induced RTP enhancement of organic dyes, thus laying a solid foundation for the rational design of advanced RTP materials based on supramolecular assemblies.

Modulating excited state properties of thermally activated delayed fluorescence molecules by hybrid long-range and short-range charge transfer strategy

Balancing the rapid radiative decay process and the fast reverse intersystem crossing (RISC) process of thermally activated delayed fluorescence (TADF) molecule remains a great challenge and efficient molecular design strategies are highly desired. Herein, from a theoretical perspective, excited state properties of three reported TADF molecules (1TICz, 1BOICz and 2BOICz) are investigated based on density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations coupled with the thermal vibration correlation function (TVCF) method. Results indicate that, by introducing the multi-resonance (MR) acceptor, 1BOICz possesses hybrid long-range and short-range charge transfer features, balanced small energy gap (ΔEST) and large oscillator strength (f) is obtained. Furthermore, by incorporating double equivalent MR acceptors in 2BOICz, largely enhanced f with slightly changed ΔEST is achieved, inner mechanism for remarkable photophysical property is illustrated. Keep this strategy, seven new TADF molecules (2pDBA-bICz-1, 2pDBA-bICz-2, 2OSBA-bICz, 2DQAO-bICz, 2QAO-bICz, 2SQAO-bICz and 2OQAO-bICz) are theoretically designed, detailed physical parameters are analyzed and excited state energy consumption process is studied. Strong electrophilicity on acceptor is determined and the strength of nucleophilic sites on the bridge-phenyl of 2DQAO-bICz, 2QAO-bICz, 2SQAO-bICz and 2OQAO-bICz is increased, this promotes the short-range charge transfer property. In addition, the excitation processes for all studied molecules are dominated by long-range charge transfer from donor to acceptors, and supplemented by the short-range charge transfer on the bridge-phenyl with MR effect. Compromise energy gap and oscillator strength as well as large spin orbit coupling (SOC) constant are obtained for designed molecules. Thus, by regulating the long-range and short-range charge transfer ratios, excited state properties are successfully modulated and new efficient TADF molecules are proposed. Our research aims to provide deeper insight into long-range and short-range charge transfer features in balancing small ΔEST and large f, which could facilitate the development of novel efficient TADF molecules.

Theoretical Insight into the Effect of Phosphorus Oxygenation on Nonradiative Decays: Comparative Analysis of P-Bridged Stilbene Analogs.

Incorporation of the phosphorus element into a π-conjugated skeleton offers valuable prospects for adjusting the electronic structure of the resulting functional π-electron systems. Trivalent phosphorus has the potential to decrease the LUMO level through σ*-π* interaction, which is further enhanced by its oxygenation to the pentavalent P center. This study shows that utilizing our computational analysis to examine excited-state dynamics based on radiative/nonradiative rate constants and fluorescence quantum yield (ΦF) is effective for analyzing the photophysical properties of P-containing organic dyes. We theoretically investigate how the trivalent phosphanyl group and pentavalent phosphine oxide moieties affect radiative and nonradiative decay processes. We evaluate four variations of P-bridged stilbene analogs. Our analysis reveals that the primary decay pathway for photoexcited bis-phosphanyl-bridged stilbene is the intersystem crossing (ISC) to the triplet state and nonradiative. The oxidation of the phosphine moiety, however, suppresses the ISC due to the relative destabilization of the triplet states. The calculated rate constants match an increase in experimental ΦF from 0.07 to 0.98, as simulated from 0.23 to 0.94. The reduced HOMO-LUMO gap supports a red shift in the fluorescence spectra relative to the phosphine analog. The thiophene-fused variant with the nonoxidized trivalent P center exhibits intense emission with a high ΦF, 0.95. Our prediction indicates that the ISC transfer is obstructed owing to the relatively destabilized triplet state induced by the thiophene substitution. Conversely, the thiophene-fused analog with the phosphine oxide moieties triggers a high-rate internal conversion mediated by conical intersection, leading to a decreased ΦF.

Unraveling the Marked Differences of the Excited-State Properties of Arylgold(III) Complexes with C∧N∧C Tridentate Ligands.

Three structurally similar gold(III) complexes with C∧N∧C tridentate ligands, [1; C∧N∧C = 2,6-diphenylpyridine], [2; C∧N∧C = 2,6-diphenylpyrazine], and [3; C∧N∧C = 2,6-diphenyltriazine], have been investigated theoretically to rationalize the marked difference in emission behaviors. The geometrical and electronic structures, spectra properties, radiative and nonradiative decay processes, as well as reverse intersystem crossing and reverse internal conversion (RIC) processes were thoroughly analyzed using density functional theory (DFT) and time-dependent DFT calculations. The computed results indicate that there is a small energy difference between the lowest-energy triplet state (T1) and the second lowest-energy triplet state (T1') of complexes 2 and 3, suggesting that the excitons in the T1 state can reach the emissive higher-energy T1' through the RIC process. In addition, the non-emissive T1 states of gold(III) complexes in solution can be ascribed to the easily accessible metal-centered (3MC) state or possibly tunneling into high-energy vibrationally excited singlet states for nonradiative decay. The low efficiency of 3 is attributed to the deactivation pathway via the 3MC state. The present study elucidates the relationship between structure and property of gold(III) complexes featuring C∧N∧C ligands and providing a comprehensive understanding of the significant differences in their luminescence behaviors.

Improvement in Radiative Efficiency Via Intramolecular Charge Transfer in ortho-Carboranyl Luminophores Modified with Functionalized Biphenyls.

In this study, we found that the electronic effects of the functional groups on aromatic units attached to o-carboranyl species can enhance the efficiency of intramolecular charge transfer (ICT)-based radiative decay processes. Six o-carboranyl-based luminophores having attached functionalized biphenyl groups with CF3, F, H, CH3, C(CH3)3, and OCH3 substituents were prepared and fully characterized by multinuclear magnetic resonance spectroscopy. In addition, their molecular structures were determined by single-crystal X-ray diffractometry, which revealed that the distortion of the biphenyl rings and the geometries around the o-carborane cages were similar. All compounds exhibited ICT-based emissions in the rigid state (solution at 77 K and film). Intriguingly, the quantum efficiencies (Φem) of five compounds (that of the group with CF3 could not be measured because of its extremely weak emissions) in the film state increased gradually as the electron-donating power of the terminal functional group modifying the biphenyl moiety increased. Furthermore, the nonradiative decay constants (knr) for the group with OCH3 were estimated to be one-tenth of those for the group with F, whereas the radiative decay constants (kr) for the five compounds were similar. The dipole moments (μ) calculated for the optimized first excited state (S1) structures gradually increased, from that of the group with CF3 to that of the group with OCH3, implying that the inhomogeneity of the molecular charge distribution was enhanced by electron donation. The electron-rich environment formed as a result of electron donation led to efficient charge transfer to the excited state. Both experimental and theoretical findings revealed that the electronic environment of the aromatic moiety in o-carboranyl luminophores can be controlled to accelerate or interrupt the ICT process in the radiative decay of excited states.

Deep blue thermally activated delayed fluorescent emitters based on methyl-modified acridin-9(10H)-one acceptor

Developing deep blue thermally activated delayed fluorescence (TADF) materials with high efficiencies and good color purities is still a formidable challenge. Here, two novel deep blue TADF emitters, namely MePhCz-AD and MePhCz-AD-Py, were synthesized by incorporating two 3,6-diphenyl-9H-carbazole donors onto the methyl-modified acridin-9(10H)-one (AD) acceptor, respectively. The high rigidity of AD acceptor effectively suppressed non-radiative transition and vibration relaxation of excited states, which is favorable for a good emitting quantum yield and narrow spectral width. The presence of methyl groups at 2,7-sites of AD ring slightly reduced the acceptor strength and contributed to the deep blue emission color. Incorporation of phenyls at 3,6-sites of carbazole ring delocalized the distribution of the highest occupied molecular orbital (HOMO), promoting the radiative decay process. As a result, these two emitters showed deep blue TADF with fast radiative decay rates kR > 107 s−1. In addition, with the introduction of pyridyl (Py) group at 10-site of AD ring instead of phenyl, both the spin-orbital coupling (SOC) constant between high-lying triplet states and the lowest singlet excited state (S1) and thus the reverse intersystem crossing rate constant (kRISC) were dramatically promoted for MePhCz-AD-Py. The organic light-emitting diode with MePhCz-AD-Py as doped emitter exhibited a maximum external quantum efficiency (EQEmax) of 15.4% with a relatively narrow FWHM of 60 nm and the deep-blue color coordinates of (0.15, 0.15).

Approaching the Shortest Intermetallic Distance of Half‐Lantern Diplatinum(II) Complexes for Efficient and Stable Deep‐Red Organic Light‐Emitting Diodes

AbstractA fast radiative decay process for long‐wavelength molecular light‐emitters is vital to achieving a high emission efficiency by outcompeting the nonradiative decay imposed by the energy‐gap law. An ensuing short emission lifetime is also beneficial for fabricating high‐performance organic light‐emitting diodes. Herein a series of half‐lantern dinuclear platinum(II) complexes is reported, which shows high‐efficiency deep red phosphorescence (λem > 660 nm). The molecules are designed to have a cofacially aligned structure featuring short Pt–Pt distances of 2.80–2.83 Å by using 10H‐pyrido[3,2‐b][1,4]benzoxazine (PyXZ) as the rigid bridges, which are revealed by single crystal X‐ray diffraction analysis. Together with the strong electron‐donating property of PyXZ bridges, the metallophilic interaction endows low‐energy triplet excited states with mixed metal–metal‐to‐ligand charge‐transfer (3MMLCT) and ligand‐to‐ligand charge‐transfer (3LLCT) characters. The deep red devices based on the diplatinum(II) complexes show maximum external quantum efficiencies (EQEs) up to 21.8%. The EQE of 19.4% and operational lifetime (LT85) of 334 h (the operational time after which the luminance drops to 85% of the initial value) at a luminance of 1000 cd m−2 promise the pratical use of these complexes.

Orientation-Dependent Image Dipole Interaction for the Tuning of the Excitonic Properties of CdSe Nanoplatelets

The fundamental characteristics of semiconductor nanoplatelets (NPLs) have been intensively studied with a view to their use in various optoelectronic devices. In particular, the assembly of highly anisotropic NPLs into stacks allows their optical properties to be easily controlled. Here, we systematically investigate the radiative decay processes of NPL assemblies for two distinct configurations, face-down and edge-up, and find a new way of manipulating their excitonic properties by introducing metamaterial structures. While the exciton lifetime for face-down NPLs is not strongly affected by the metamaterials, a significant reduction in the exciton lifetime for edge-up NPLs is observed. We account for this interesting result in terms of orientation-dependent image dipole interactions by showing that the net transition dipole moments for the two NPL configurations can be affected inversely by metamaterials. These results will facilitate the development of optoelectronic applications requiring the active manipulation of exciton lifetimes.

Theoretical investigation of the influence of heterocycles on the radiative and non-radiative decay processes of iridium(iii) complexes

By means of density functional theory and time-dependent density functional theory, the radiative and non-radiative decay processes of iridium(iii) complexes are investigated to explore the role of N-heterocyclic moieties in chelating ligands.

Computational investigation of graphene quantum dot and tridentate Au(iii) complex composites

We studied Au(iii) complex decay using DFT and TDDFT to understand the impact of graphene quantum dot (GQD) ligands on emission properties and phosphorescence quantum yields.

Highly emissive 4-carbazole-appended salen-indium complex: the effect of strong donor-acceptor interaction.

Herein, we report our findings on 4-carbazole (CBZ)-appended salen-based indium complexes, CBZIn1 and CBZIn2, which feature diimine bridges exhibiting different electron-accepting properties. Notably, CBZIn2 exhibited a significantly higher photoluminescence quantum efficiency (PLQY, ΦPL) in toluene than CBZIn1, with a value over 15 times greater (ΦPL = 57.7% for CBZIn2; ΦPL = 3.7% for CBZIn1). In particular, in the rigid state of THF at 77 K, CBZIn2 exhibited a near-unity PLQY of 98.2%. Even in the PMMA film, CBZIn2 maintained a high level of PLQY (ΦPL = 70.2%). These results can be attributed to the highly efficient radiative decay process based on intramolecular charge-transfer (ICT) transition between the moderately twisted CBZ, characterized by its conformational rigidity and the 1,2-dicyanoethylene-bridged salen, which exhibits a strong electron-accepting ability. Furthermore, these findings are supported by theoretical calculations.

Deciphering competing radiative relaxation pathways observed in Pr3+-Activated yttrium-based compounds: UV emission versus visible emission

Pr3+-activated yttrium-based compounds have garnered significant research interest as the electronic transition of Pr3+ dopant incorporated in host lattices are quite versatile, giving rise to the production of either UV or visible electromagnetic radiation. The tunable 5d orbital energy level of Pr3+ with an electronic configuration [Xe]4f15d1 depending on the external crystal fields, coordinating anion ligands (mainly determined by covalency of anion ligands), and symmetry of crystal structures can indeed control the radiative decay processes whether to generate UV or self-trapped exciton-mediated visible emission. We have investigated three different Pr3+-activated crystals of YPO4, YBO3, and Y2SiO5 using two different excitation processes including direct host lattice excitation (cathodoluminescence: CL) and f-d excitation of Pr3+ dopants (photoluminescence: PL). Such radiative decay mechanism observed in Pr3+-doped yttrium-based compounds has been deciphered that photoexcitation of Pr3+ ions results in 4f15d1→4f2 electronic transition with UV emission (PL) whereas above-bandgap excitation of host lattices brings about the efficient production of visible emission mediated through self-trapped excitons (CL). When changing the anion sublattices, the emission peak corresponding to 4f15d1→4f2 transition shifted to longer wavelength as a result of modulated covalency and crystal field strength. As the host lattices changes as a function of anion sublattices, the bandgap reduced from 8.6 eV (for YPO4) to 7.6 eV (for YBO3) and to 6.1 eV (for Y2SiO5), directly influencing rate of trapping of exciton and their formation of self-trapped exciton, which further give rise to production of the self-trapped exciton mediated visible emission. The fundamental understanding of the multiple, radiative relaxation pathways provides a designing principle for achieving more efficient UV emitting phosphors (at the same time by suppressing visible emission or vice versa) for germicidal and medical applications.

Spin-Orbit Coupling Calculation Combined with the Reference Interaction Site Model Self-Consistent Field Explicitly Including Constrained Spatial Electron Density Distribution.

Studying the radiative and non-radiative decay processes of molecules in a solution is an important issue in the design of organic and functional molecules. Theoretical approaches have great potential for revealing this decay process through computation of various parameters, such as the energy surfaces at the excited state and spin-orbit coupling (SOC). The development of quantum chemical programs has enabled the calculation of SOC values to become popular for the gas phase. However, SOC calculations in solution have some difficulties that need to be overcome. In the present study, the authors combined the SOC calculations with the reference interaction site model self-consistent field explicitly including constrained spatial electron density distribution. To validate the reliability of our method, the decay process of dimethylaminobenzonitrile in cyclohexane and acetonitrile was studied. By computing the SOC values in both solution systems, the authors were able to investigate the decay process at the atomistic level. Furthermore, a natural transition orbital analysis and the measurement of the decomposed SOC values were found to provide a clear understanding of intersystem crossing.

Effect of structural modifications on the spectral and lasing characteristics of truxene-cored starbursts with/without diphenylamine end-cappers

This study examined the effect of chemical modifications on the spectral and lasing characteristics of truxene-cored starbursts as gain media for organic lasers. A series of conjugated starburst materials, consisting of a truxene core and oligofluorene bridges with and without diphenylamine (DPA), namely, TrXD and TrX, were assessed as model molecules to investigate the influence of DPA on the photophysical characteristics and organic lasing behaviors. TrXD with DPA could effectively restrain the aggregation and greatly suppress the aggregation-induced emission quenching, yielding high photoluminescence efficiency. A higher radiative decay rate kr was observed for TrXD than for TrX, suggesting that DPA is beneficial for enhancing the radiative decay process. TrXD showed low amplified spontaneous emission thresholds of 2.1–4.3 μJ cm−2 with high net gain coefficients of 80–101 cm−1, rather low loss coefficients of 2.6–4.4 cm−1, compared with TrX. The best performance with a lasing threshold of 0.31 kW cm−2 was obtained for Tr3D, which was superior to that of Tr3 (0.86 kW cm−2). The molecular systems with DPA have a large potential as attractive molecules for organic lasers because of the superior lasing properties induced by kr.

Study of the rare decay at the BESIII * *Supported by the National Natural Science Foundation of China (12135013), and in part by National Key Research and Development Program of China (2020YFA0406400)

The two-photon radiative decay process was studied, and the main contribution processes, and , were calculated. With the specific conditions at the BESIII, this rare decay process and the main background process were investigated. The results show that the ratio of signal to background can reach 1.24 with optimized selection criteria at the BESIII. In addition, distributions of the signal and background are presented. All the results show that the signal is large enough to be experimentally measured.

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.

Crucial Factors Regulating Intramolecular Charge-Transfer-Based Radiative Efficiency in ortho-Carboranyl Luminophores: Planarity between Substituted Biphenyl Rings.

o-Carboranyl compounds contain specific geometries, ranging from planar to orthogonally distorted biphenyl rings. Herein, 13 o-carboranyl compounds, 1HF–13PP, were synthesized and fully characterized to determine the impact of structural formation of the aromatic group appended with the o-carborane to estimate the efficiency of their radiative decay process. All the compounds exhibited significant intramolecular charge transfer (ICT)-based emission in the crystalline state at 298 K. Remarkably, increasing the distorted dihedral angles between biphenyl rings gradually decreased the emission efficiencies. Furthermore, their radiative decay constants decreased linearly with increasing dihedral angles, which demonstrated the inversely proportional relationship between these two factors. These findings distinctly suggest that the planar or distorted geometry of substituted aryl groups can strongly affect the efficiency of the ICT-based radiative process in o-carboranyl luminophores.

Investigate the Relationship between Structure and Triplet Potential Energy Surface to Control the Phosphorescence Quantum Yield of Platinum(II) Complex: A Theoretical Investigation.

Triplet potential energy surfaces are extremely important for phosphors because they are closely related to radiative and nonradiative decay processes. In this article, the correlations between the strctures and the triplet potential energy surfaces for Pt(II) complexes are investigated in detail with the help of density functional theory (DFT). The calculated results indicate that triplet hypersurface minima with different configurations, i.e., planar and bent, rely on the geometries of the platinum(II) complex. A bent configuration could cause an obvious decrease in the phosphorescence quantum yield, and an unusual low-lying triplet excited-state decay route is proposed. In addition, the extension of π-conjugation and addition of suitable substituents, for example arylboron, are promising strategies for changing the triplet hypersurface to achieve the minimum with a planar configuration, leading to a high phosphorescence quantum yield. Moreover, to predict the triplet hypersurface, a useful and simple strategy has been put forward. In our study, the relationship between the structure and the lowest-lying triplet potential energy surface of a Pt(II) complex is constructed, which is significant and meaningful for controlling the phosphorescence quantum yield to design high-performance phosphorescent materials used in the field of organic light-emitting diodes (OLEDs).