Spin-vibronic Coupling Research Articles

Enhancing Spin-Orbit Coupling in an Indolocarbazole Multiresonance Emitter by a Sulfur-Containing Peripheral Substituent for a Fast Reverse Intersystem Crossing.

A fast reverse intersystem crossing (RISC) remains an ongoing pursuit for multiresonance (MR) emitters but faces formidable challenges, particularly for indolocarbazole (ICz) derived ones. Here, heavy-atom effect is introduced first to construct ICz-MR emitter using a sulfur-containing substitute, simultaneously enhancing both spin-orbit and spin-vibronic coupling to afford a fast RISC with a rate of 1.2×105s-1, nearly one order of magnitude higher than previous maximum values. The emitter also exhibits an extremely narrow deep-blue emission peaking at 456nm with full-width at half-maxima of merely 12nm and a photoluminescence quantum yield of 92%. Benefiting from its efficient triplet upconversion capability, this emitter achieves not only a high maximum external quantum efficiency (EQE) of 31.1% in organic light-emitting diodes but also greatly alleviates efficiency roll-off, affording record-high EQEs of 29.9% at 1000cdm-2 and 18.7% at 5000cdm-2 among devices with ICz-MR emitters.

Highly efficient pure-blue organic light-emitting diodes based on rationally designed heterocyclic phenophosphazinine-containing emitters

Multi-resonance thermally activated delayed fluorophores have been actively studied for high-resolution photonic applications due to their exceptional color purity. However, these compounds encounter challenges associated with the inefficient spin-flip process, compromising device performance. Herein, we report two pure-blue emitters based on an organoboron multi-resonance core, incorporating a conformationally flexible donor, 10-phenyl-5H-phenophosphazinine 10-oxide (or sulfide). This design concept selectively modifies the orbital type of high-lying excited states to a charge transfer configuration while simultaneously providing the necessary conformational freedom to enhance the density of excited states without sacrificing color purity. We show that the different embedded phosphorus motifs (phosphine oxide/sulfide) of the donor can finely tune the electronic structure and conformational freedom, resulting in an accelerated spin-flip process through intense spin-vibronic coupling, achieving over a 20-fold increase in the reverse intersystem crossing rate compared to the parent multi-resonance emitter. Utilizing these emitters, we achieve high-performance pure-blue organic light-emitting diodes, showcasing a top-tier external quantum efficiency of 37.6% with reduced efficiency roll-offs. This proposed strategy not only challenges the conventional notion that flexible electron-donors are undesirable for constructing narrowband emitters but also offer a pathway for designing efficient narrow-spectrum blue organic light-emitting diodes.

The direct role of nuclear motion in spin-orbit coupling in strongly correlated spin systems.

The interaction between the magnetic moment of an electron and the magnetic field generated by a moving charge is one component of the spin-orbit interaction. The nuclei in a molecule or solid are charged, are generally in vibrational motion, and so contribute to this interaction, but the direct coupling between nuclear momentum and electron spin is normally ignored in discussions of spin-forbidden phenomena such as transitions between states of different spin, even when the nuclei are recognized as playing a fundamental role (spin-vibronic coupling). Here, we investigate the spin-orbit interaction in a Heisenberg model interacting with vibrating point charges representing nearby bridging ligands. To reach the model, we apply second order perturbation theory to the Hubbard model with the spin-orbit interaction. In contrast to the other components of the spin-orbit interaction, the part that directly couples the momentum of the charge and electron spin appears at first order as an effective magnetic field at each site. We find that the inclusion of this nuclear-motion induced spin-orbit coupling can increase the rate of otherwise spin-forbidden transitions between different spin states of the Heisenberg model by many orders of magnitude. This overlooked interaction may, therefore, play a significant role in spin-forbidden phenomena such as spin relaxation in coupled spin-qubits.

Extended theoretical modeling of reverse intersystem crossing for thermally activated delayed fluorescence materials.

Thermally activated delayed fluorescence (TADF) materials and multi-resonant (MR) variants are promising organic emitters that can achieve an internal electroluminescence quantum efficiency of ~100%. The reverse intersystem crossing (RISC) is key for harnessing triplet energies for fluorescence. Theoretical modeling is thus crucial to estimate its rate constant (kRISC) for material development. Here, we present a comprehensive assessment of the theory for simulating the RISC of MR-TADF molecules within a perturbative excited-state dynamics framework. Our extended rate formula reveals the importance of the concerted effects of nonadiabatic spin-vibronic coupling and vibrationally induced spin-orbital couplings in reliably determining kRISC of MR-TADF molecules. The excited singlet-triplet energy gap is another factor influencing kRISC. We present a scheme for gap estimation using experimental Arrhenius plots of kRISC. Erroneous behavior caused by approximations in Marcus theory is elucidated by testing 121 MR-TADF molecules. Our extended modeling offers in-depth descriptions of kRISC.

Heavy-atom-free BODIPY dendrimer: utilizing the spin-vibronic coupling mechanism for two-photon photodynamic therapy in zebrafish.

In this study, the heavy-atom-free BODIPY dendrimer TM4-BDP was synthesized for near-infrared photodynamic therapy, and was composed of a triphenylamine-BODIPY dimer and four 1-(2-morpholinoethyl)-1H-indole-3-ethenyl groups. The TM4-BDP could achieve near-infrared photodynamic therapy through two different photosensitive pathways, which include one-photon excitation at 660 nm and two-photon excitation at 1000 nm. In the one-photon excitation pathway, the TM4-BDP could generate singlet oxygen and superoxide radicals under 660 nm illumination. In addition, the one-photon PDT experiment in human nasopharyngeal carcinoma (CNE-2) cells also indicated that the TM4-BDP could specifically accumulate in lysosomes and show great cell phototoxicity with an IC50 of 22.1 μM. In the two-photon excitation pathway, the two-photon absorption cross-section at 1030 nm of TM4-BDP was determined to be 383 GM, which means that it could generate reactive oxygen species (ROS) under 1000 nm femtosecond laser excitation. Moreover, the two-photon PDT experiment in zebrafish also indicated the TM4-BDP could be used for two-photon fluorescence imaging and two-photon induced ROS generation in biological environments. Furthermore, in terms of the ROS generation mechanism, the TM4-BDP employed a novel spin-vibronic coupling intersystem crossing (SV-ISC) process for the mechanism of ROS generation and the femtosecond transient absorption spectra indicated that this novel SV-ISC mechanism was closely related to its charge transfer state lifetime. These above experiments of TM4-BDP demonstrate that the dendrimer design is an effective strategy for constructing heavy-atom-free BODIPY photosensitizers in the near-infrared region and lay the foundation for two-photon photodynamic therapy in future clinical trials.

Spin-Vibronic Coupling Controls the Intersystem Crossing of Iodine-Substituted BODIPY Triplet Chromophores.

4,4-Difluoro-4-borata-3a-azonia-4a-aza-s-indacene (BODIPY) dyes are extensively used in various applications of their triplet states, ranging from photoredox catalysis, through triplet sensitization to photodynamic therapy. However, the rational design of BODIPY triplet chromophores by ab initio modelling is limited by their strong interactions of spin, electronic and vibrational dynamics. In particular, spin-vibronic coupling is often overlooked when estimating intersystem crossing (ISC) rates. In this study, a combined experimental and theoretical approach using spin-vibronic coupling to correctly describe ISC in BODIPY dyes was developed. For this purpose, seven π-extended BODIPY derivatives with iodine atoms in different positions were examined. It was found that the heavy-atom effect of iodine atoms is site specific, causing high triplet yields in only some positions. This site-specific ISC was explained by El-Sayed rules, so both the contribution and character of the molecular orbitals involved in the excitation must be considered when predicting the ISC rates. Overall, the rational design of BODIPY triplet chromophores requires using (i) the high-quality electronic structure theory, including both static and dynamical correlations; and (ii) the two-component wave function Hamiltonian, and rationalizing; and (iii) ISC based on the character of the molecular orbitals of heavy atoms involved in the excitation, expanding El-Sayed rules beyond their traditional applications.

Theoretical spectroscopy for unraveling the intensity mechanism of the optical and photoluminescent spectra of chiral Re(I) transition metal complexes.

In this work, we present a computational study that is able to predict the optical absorption and photoluminescent properties of the chiral Re(I) family of complexes [fac-ReX(CO)3L], where X is either Cl or I and L is N-heterocyclic carbene extended with π-conjugated [5]-helicenic unit. The computational strategy is based on carefully calibrated time dependent density functional theory calculations and operates in conjunction with an excited state dynamics approach to treat in addition to absorption (ABS) and photoluminescence (PL), electronic circular dichroism (ECD), and circularly polarized luminescence (CPL) spectroscopies, respectively. The employed computational approach provides, an addition, access to the computation of phosphorescence rates in terms of radiative and non-radiative relaxation processes. The chosen molecules consist of representative examples of non-helicenic (NHC) and helicenic diastereomers. The agreement between theoretical and experimental spectra, including absorption (ABS, ECD) and emission (PL, CPL), is excellent, validating a quantitative interpretation of the spectral features on the basis of natural transition orbitals and TheoDore analyses. It is demonstrated that across the set of studied Re(I) diastereomers, the emission process in the case of NHC diastereomers is metal to ligand charge transfer in nature and is dominated by the easy-axis anisotropy of the emissive excited multiplet. On the contrary, in the cases of the helicenic diastereomers, the emission process is intra ligand charge transfer in nature and is dominated by the respective easy-plane anisotropy of the emissive excited multiplet. This affects remarkably the photoluminescent properties of the molecules in terms of PL and CPL spectral band shapes, spin-vibronic coupling, relaxation times, and the respective quantum yields. Spin-vibronic coupling effects are investigated at the level of the state-average complete active space self-consistent field in conjunction with quasi-degenerate second order perturbation theory. It is in fact demonstrated that a spin-vibronic coupling mechanism controls the observed photophysics of this class of Re(I) complexes.

Hybridization of short-range and long-range charge transfer excited states in multiple resonance emitter

Multiple resonance (MR) thermally activated delayed fluorescence emitters have been actively studied as pure blue dopants for organic light-emitting diodes (OLEDs) because of excellent color purity and high efficiency. However, the reported MR emitter, 2,5,13,16-tetra-tert-butylindolo[3,2,1-jk]indolo[1′,2′,3′:1,7]indolo[2,3-b]carbazole (tDIDCz) based on bis-fused indolocarbazole framework could not demonstrate efficient triplet-to-singlet spin crossover. In this work, we report two isomeric MR emitters designed to promote triplet exciton harvesting by reconstructing the electronic structure of tDIDCz. To manage excited states, strong electron donors were introduced at the 2,5-/1,6-position of tDIDCz. As a result, 2,5-positions managed tDIDCz shows long-range charge transfer characteristics while preserving the MR nature. Quantum chemical calculation demonstrates direct spin-orbit coupling by long-range charge transfer and spin-vibronic coupling assisted reverse intersystem crossing by short-range charge transfer simultaneously contribute to triplet-to-singlet spin crossover. Consequently, high performance blue OLED recorded a high external quantum efficiency of 30.8% at a color coordinate of (0.13, 0.13).

Long-Lived Charge-Separated State in Naphthalimide-Phenothiazine Compact Electron Donor-Acceptor Dyads: Effect of Molecular Conformation Restriction and Solvent Polarity.

To study the charge separation (CS) and long-lived CS state, we prepared a series of dyads based on naphthalimide (NI, electron acceptor) and phenothiazine (PTZ, electron donor), with an intervening phenyl linker attached on the N-position of both moieties. The purpose is to exploit the electron spin control effect to prolong the CS-state lifetime by formation of the 3CS state, instead of the ordinary 1CS state, the spin-correlated radical pair (SCRP), or the free ion pairs. The electronic coupling magnitude is tuned by conformational restriction exerted by the methyl groups on the phenyl linker. Differently from the previously reported NI-PTZ analogues containing long and flexible linkers, we observed a significant CS emission band centered at ca. 600 nm and thermally activated delayed fluorescence (TADF) with a lifetime of 13.8 ns (population ratio: 42%)/321.6 μs (56%). Nanosecond transient absorption spectroscopy indicates that in cyclohexane (CHX), only the 3NI* state was observed (lifetime τ = 274.7 μs), in acetonitrile (ACN), only the CS state was observed (τ = 1.4 μs), whereas in a solvent with intermediate polarity, such as toluene (TOL), both the 3NI* (shorter-lived) and the CS states were observed. Observation of the long-lived CS state in ACN, yet lack of TADF, confirms the spin-vibronic coupling theoretical model of TADF. Femtosecond transient absorption spectroscopy indicates that charge separation occurs in both nonpolar and polar solvents, with time constants ranging from less than 1 ps in ACN to ca. 60 ps in CHX. Time-resolved electron paramagnetic resonance (TREPR) spectra indicate the existence of the 3NI* and CS states for the dyads upon photoexcitation. The electron spin-spin dipole interaction magnitude of the radical anion and cation of the CS state is intermediate between that of a typical SCRP and a 3CS state, suggesting that the long CS-state lifetime is partially due to the electron spin control effect.

The effect of dark states on the intersystem crossing and thermally activated delayed fluorescence of naphthalimide-phenothiazine dyads.

A series of 1,8-naphthalimide (NI)-phenothiazine (PTZ) electron donor-acceptor dyads were prepared to study the thermally activated delayed fluorescence (TADF) properties of the dyads, from a point of view of detection of the various transient species. The photophysical properties of the dyads were tuned by changing the electron-donating and the electron-withdrawing capability of the PTZ and NI moieties, respectively, by oxidation of the PTZ unit, or by using different aryl substituents attached to the NI unit. This tuning effect was manifested in the UV-vis absorption and fluorescence emission spectra, e.g., in the change of the charge transfer absorption bands. TADF was observed for the dyads containing the native PTZ unit, and the prompt and delayed fluorescence lifetimes changed with different aryl substituents on the imide part. In polar solvents, no TADF was observed. For the dyads with the PTZ unit oxidized, no TADF was observed as well. Femtosecond transient absorption spectra showed that the charge separation takes ca. 0.6 ps, and admixtures of locally excited (3LE) state and charge separated (1CS/3CS) states formed (in n-hexane). The subsequent charge recombination from the 1CS state takes ca. 7.92 ns. Upon oxidation of the PTZ unit, the beginning of charge separation is at 178 fs and formation of 3LE state takes 4.53 ns. Nanosecond transient absorption (ns-TA) spectra showed that both 3CS and 3LE states were observed for the dyads showing TADF, whereas only 3LE or 3CS states were observed for the systems lacking TADF. This is a rare but unambiguous experimental evidence that the spin-vibronic coupling of 3CS/3LE states is crucial for TADF. Without the mediating effect of the 3LE state, no TADF is resulted, even if the long-lived 3CS state is populated (lifetime τCS ≈ 140 ns). This experimental result confirms the 3CS → 1CS reverse intersystem crossing (rISC) is slow, without coupling with an approximate 3LE state. These studies are useful for an in-depth understanding of the photophysical mechanisms of the TADF emitters, as well as for molecular structure design of new electron donor-acceptor TADF emitters.

Activating Molecular Room-Temperature Phosphorescence by Manipulating Excited-State Energy Levels in Poly(vinyl alcohol) Matrix.

Poly(vinyl alcohol) (PVA) has been found as a wonderful matrix for chromophores to boost their room-temperature phosphorescence (RTP) character by forming abundant hydrogen bonding. Despite the well-utilized protective effect, the constructive role in accelerating the intersystem crossing is less investigated. Here, we focus on its role in manipulating the excited-state energy level to facilitate multiple intersystem crossing channels. Six benzoyl carbazole derivatives do not emit RTP in their solutions, powders, or crystals but exhibit significantly persistent RTP signals when embedded into the PVA matrix. Charge-transfer excited states were trapped by cofacial stacking in crystal, which blocks the intersystem crossing channels. In the PVA matrix, the allowed broad distribution of charge-transfer states covers the locally excited states, offering multiple intersystem crossing pathways via spin-vibronic orbit coupling. Consequently, efficient and persistent heavy-atom-free phosphors have been developed with the highest quantum yields of 7.7% and the longest lifetime of 2.3 s.

Color Stable Deep Blue Multi-Resonance Organic Emitters with Narrow Emission and High Efficiency.

The development of highly efficient and deep blue emitters satisfying the color specification of the commercial products has been a challenging hurdle in the organic light-emitting diodes (OLEDs). Here, deep blue OLEDs with a narrow emission spectrum with good color stability and spin-vibronic coupling assisted thermally activated delayed fluorescence are reported using a novel multi-resonance (MR) emitter built on a pure organic-based molecular platform of fused indolo[3,2,1-jk]carbazole structure. Two emitters derived from 2,5,11,14-tetrakis(1,1-dimethylethyl)indolo[3,2,1-jk]indolo[1',2',3':1,7]indolo[3,2-b]carbazole (tBisICz) core are synthesized as the MR type thermally activated delayed fluorescence emitters realizing a very narrow emission spectrum with a full-width-at-half-maximum (FWHM) of 16nm with suppressed broadening at high doping concentration. The tBisICz core is substituted with a diphenylamine or 9-phenylcarbazole blocking group to manage the intermolecular interaction for high efficiency and narrow emission. The deep blue OLEDs achieve high external quantum efficiency (EQE) of 24.9%, small FWHM of 19nm, and deep blue color coordinate of (0.16, 0.04) with good color stability with increase in doping concentration. To the authors' knowledge, the EQE in this work is one of the highest values reported for the deep blue OLEDs that achieve the BT.2020standard.

Spin-Vibronic Control of Intersystem Crossing in Iodine-Substituted Heptamethine Cyanines.

Spin-orbit coupling between electronic states of different multiplicity can be strongly coupled to molecular vibrations, and this interaction is becoming recognized as an important mechanism for controlling the course of photochemical reactions. Here, we show that the involvement of spin-vibronic coupling is essential for understanding the photophysics and photochemistry of heptamethine cyanines (Cy7), bearing iodine as a heavy atom in the C3' position of the chain and/or a 3H-indolium core, as potential triplet sensitizers and singlet oxygen producers in methanol and aqueous solutions. The sensitization efficiency was found to be an order of magnitude higher for the chain-substituted than the 3H-indolium core-substituted derivatives. Our ab initio calculations demonstrate that while all optimal structures of Cy7 are characterized by negligible spin-orbit coupling (tenths of cm-1) with no dependence on the position of the substituent, molecular vibrations lead to its significant increase (tens of cm-1 for the chain-substituted cyanines), which allowed us to interpret the observed position dependence.

Insights into the phototautomerism of free-base 5, 10, 15, 20-tetrakis(4-sulfonatophenyl) porphyrin.

Phototautomerism in the excited states of free-base 5, 10, 15, 20-tetrakis(4-sulfonatophenyl) porphyrin (H2TPPS4-) has been investigated combining, for the first time, advanced Electron Paramagnetic Resonance (EPR) with fluorescence and Raman spectroscopy. Triplet EPR spectroscopy, performed in protic and deuterated solvents and in the presence of photoselection, confirms the occurrence of phototautomerization and additionally suggests the formation of the cis tautomer as a minor component. The zero-field splitting parameters and triplet sublevel populations indicate that the process is slow in the triplet state. The results obtained by EPR combined with photoselection and fluorescence anisotropy have been interpreted within a model which accounts for a fast trans-trans tautomerization promoted by a spin-vibronic coupling mechanism for intersystem crossing, with an even distribution of the two trans tautomers at liquid nitrogen temperatures for H2TPPS4-.

Ultrafast T[formula omitted] generation in pyrene-4,5-dione and pyrene-4,5,9,10-tetrone

Intersystem crossing pathways associated with the ultrafast generation of the lowest triplet state (T1) of pyrene-4,5-dione (PD) and pyrene-4,5,9,10-tetrones (PT) are studied with the aid of quantum chemistry and quantum dynamics simulations. Both these molecules exhibit a rapid relaxation to dark (dipole-forbidden) S1 upon populating higher bright (dipole-allowed) singlet excited states. The S1-T3 pathway is responsible for the T3 generation via the direct spin–orbit coupling in PD and the vibrational coordinate-dependent spin-vibronic coupling in PT. A rapid T3 to T1 internal conversion is observed in these molecules. The photosensitization abilities of these molecules are discussed based on the efficiency of the T3 state formation and its decay to T1 state.

Frontispiece: Detection of the Dark States in Thermally Activated Delayed Fluorescence (TADF) Process of Electron Donor‐Acceptor Dyads: Insights from Optical Transient Absorption Spectroscopy

Unraveling the complicated photophysics of thermally activated delayed fluorescence (TADF) compounds is not a trivial task, although it is critical to improve the performance of TADF emitters in OLED. In the Review by Zhao and colleagues (DOI: 10.1002/chem.202203737), recent developments of using the transient optical spectroscopic methods to study the photophysics of TADF emitters are summarized, e. g. the manifestation of the theoretically proposed spin-vibronic coupling effect and the three-state model describing the reverse intersystem crossing (RISC) in time-resolved transient absorption spectra.

Spin-vibronic interaction induced reverse intersystem crossing: A case study with TXO-TPA and TXO-PhCz molecules.

We highlight the important roles the direct spin-orbit (DSO) coupling, the spin-vibronic (SV) coupling, and the dielectric constant of the medium play on the reverse intersystem crossing (RISC) mechanism of TXO-TPA and TXO-PhCz molecules. To understand this complex phenomenon, we have calculated the RISC rate constant, kRISC, using a time-dependent correlation function-based method within the framework of second-order perturbation theory. Our computed kRISC in two different solvents, toluene and chloroform, suggests that in addition to the DSO, a dielectric medium-dependent SV mechanism may also have a significant impact on the net enhancement of the rate of RISC from the lowest triplet state to the first excited singlet state. Whereas we have found that kRISC of TXO-TPA is mostly determined by the DSO contribution independent of the choice of the solvent, the SV mechanism contributes more than 30% to the overall kRISC of TXO-PhCz in chloroform. In toluene, however, the SV mechanism is less important for the RISC process of TXO-PhCz. An analysis of mode-specific nonadiabatic coupling (NAC) between T2 and T1 of TXO-PhCz and TXO-TPA suggests that the NAC values in certain normal modes of TXO-PhCz are much higher than those of TXO-TPA, and it is more pronounced with chloroform as a solvent. The findings demonstrate the role of the solvent-assisted SV mechanism toward the net RISC rate constant, which in turn maximizes the efficiency of thermally activated delayed fluorescence.

Multiple-Resonance Extension and Spin-Vibronic-Coupling-Based Narrowband Blue Organic Fluorescence Emitters with Over 30% Quantum Efficiency.

Achieving narrow-bandwidth emission and high external quantum efficiency (EQE) simultaneously is a challenge for next-generation blue-emitting organic light-emitting diodes (OLEDs). In this study, novel multiple-resonance thermally activated delayed fluorescence (MR-TADF) emitters are developed by fusing an indolocarbazole unit with two carbazole skeletons using para-oriented nitrogen atoms. The resulting rigid and planar π-system without electron-accepting atoms exhibits pure blue photoluminescence at 470nm, reaching a 100% quantum yield with a full-width-at-half-maximum (FWHM) of 25nm. Higher-level quantum chemistry calculations confirm an MR effect within the extended π-conjugation and an enhanced triplet-to-singlet crossover (104 s-1 ) through a reduced energy gap (ΔEST ) coupled with large spin-vibronic coupling mediated by low-lying triplet excited states. An OLED fabricated using the MR-TADF emitter with CIE color coordinates of (0.12, 0.16) exhibits a record high EQE of 30.9% and a small FWHM of 23nm. With further optimization of the device structure, a high EQE of 33.8% is achieved without additional outcoupling enhancements owing to the near-perfect horizontal alignment of the emitting dipoles.

Spin-vibronic coupling in the quantum dynamics of a Fe(III) trigonal-bipyramidal complex.

The presence of a high density of excited electronic states in the immediate vicinity of the optically bright state of a molecule paves the way for numerous photo-relaxation channels. In transition-metal complexes, the presence of heavy atoms results in a stronger spin-orbit coupling, which enables spin forbidden spin-crossover processes to compete with the spin-allowed internal conversion processes. However, no matter how effectively the states cross around the Franck-Condon region, the degree of vibronic coupling, of both relativistic and non-relativistic nature, drives the population distribution among these states. One such case is demonstrated in this work for the intermediate-spin Fe(III) trigonal-bipyramidal complex. A quantum dynamical investigation of the photo-deactivation mechanism in the Fe(III) system is presented using the multi-configurational time-dependent Hartree approach based on the vibronic Hamiltonian whose coupling terms are derived from the state-averaged complete active space self-consistent field/complete active space with second-order perturbation theory (CASPT2) calculations and spin-orbit coupling of the scalar-relativistic CASPT2 states. The results of this study show that the presence of a strong (non-relativistic) vibronic coupling between the optically bright intermediate-spin state and other low-lying states of the same spin-multiplicity overpowers the spin-orbit coupling between the intermediate-spin and high-spin states, thereby lowering the chances of spin-crossover while exhibiting ultrafast relaxation among the intermediate-spin states. In a special case, where the population transfer pathway via the non-relativistic vibronic coupling is blocked, the probability of the spin-crossover is found to increase. This suggests that a careful modification of the complex by incorporation of heavier atoms with stronger relativistic effects can enhance the spin-crossover potential of Fe(III) intermediate-spin complexes.

Vibronic Coupling Effect on the Vibrationally Resolved Electronic Spectra and Intersystem Crossing Rates of a TADF Emitter: 7-PhQAD.

Assessing and improving the performance of organic light-emitting diode (OLED) materials require quantitative prediction of rate coefficients for the intersystem crossing (ISC) and reverse ISC (RISC) processes, which are determined not only by the energy gap and the direct spin-orbit coupling (SOC) between the first singlet and triplet excited-states at a thermal equilibrium position of the initial electronic state but also by the non-Condon effects such as the Herzberg-Teller-like vibronic coupling (HTVC) and the spin-vibronic coupling (SVC). Here we apply the time-dependent correlation function approaches to quantitatively calculate the vibrationally resolved absorption and fluorescence spectra and ISC/RISC rates of a newly synthesized multiple-resonance-type (MR-type) thermally activated delayed fluorescence (TADF) emitter, 7-phenylquinolino[3,2,1-de]acridine-5,9-dione (7-PhQAD), with the inclusion of the Franck-Condon (FC), HTVC, and Duschinsky rotation (DR) effects. The SVC effect on the rates has also been approximately evaluated. We find that the experimentally measured ISC rates of 7-PhQAD originate predominantly from the vibronic coupling, consistent with the previous reports on other MR-type TADF emitters. The SVC effect on ISC rates is about 10 times larger than the HTVC effect, and the latter increases the ISC rates by more than 1 order of magnitude while it slightly affects the vibrationally resolved absorption and fluorescence spectra. The discrepancy between the theoretical and experimental results is attributed to inaccurately describing excited-states calculated by the time-dependent density functional theory as well as to not fully accounting for the complex experimental conditions. This work provides a demonstration of what proportion of ISC and RISC rate coefficients of a MR-type TADF emitter can be covered by the HTVC effect, and it opens design routes that go beyond the FC approximation for the future development of high-performance OLED devices.