Excited State Energy Research Articles

1,1'-Bis-(diphenylphosphino)ferrocene appended d8- and d10-configuration based thiosquarates: the molecular and electronic configurational insights into their sensitization and co-sensitization properties for dye sensitized solar cells.

Three new d8- and d10-configuration based 1,1'-bis-(diphenylphosphino)ferrocene (dppf) appended thiosquarates complexes with general composition [M(mtsq)2dppf] (M = Ni2+ (NiL2); Zn2+ (ZnL2) and Cd2+ (CdL2)) (mtsq = 3-ethoxycyclobutenedione-4-thiolate) have been synthesized and characterized spectroscopically as well as in case of NiL2 by single crystal X-ray diffraction technique. The single crystal X-ray analysis reveals square planar geometry around Ni(II) in NiL2, where Ni(II) coordinates with two sulfur centres of two mtsq ligands in monodentate fashion and two phosphorus of a dppf ligand in chelating mode. The supramolecular architecture of NiL2 is sustained by intermolecular C-H⋯O interactions to form one-dimensional chain. Further, the application of these newly synthesized complexes as sensitizers and co-sensitizers/co-absorbents with ruthenium based N719 sensitizer in dye-sensitized solar cells (DSSCs) have been explored. The DSSC set-up based on NiL2 offers best photovoltaic performance with photovoltaic efficiency (η) 5.12%, short-circuit current (Jsc) 11.60 mA cm-2, open circuit potential (Voc) 0.690 V and incident photon to current conversion efficiency (IPCE) 63%. In co-sensitized DSSC set-up, ZnL2 along with state-of-the-art N719 dye displays best photovoltaic performance with η 6.65%, Jsc 14.47 mA cm-2, Voc 0.729 V and IPCE 69%, thereby showing an improvement by 15.25% in photovoltaic efficiency in comparison to the photovoltaic efficiency of N719 sensitized DSSC set-up. Variation in co-sensitization behaviour have been ascribed to the differences in the excited state energy level of co-sensitizers. The ZnL2 and CdL2 have a higher energy level position than N719 dye, allowing efficient electron transfer to N719 during light irradiation, while excited state of NiL2 is lower than N719 dye, preventing photoexcited electron transfer to N719, resulting in its lowest overall efficiency among the three co-sensitized DSSC setups.

Efficient red thermally activated delayed fluorescence emitters achieved through precise control of excited state energy levels.

The variety of highly efficient red/near-infrared (NIR) materials with thermally activated delayed fluorescence (TADF) feature is extremely limited so far, and it is necessary to expand the candidate pool of excellent red/deep-red emitters. However, how to control the energy level alignment of the 1CT (singlet charge transfer) state and the 3LE (triplet local excitation) state to improve the emission efficiency of materials remains a challenge. Herein, based on our previously reported green fluorescent material 67dTPA-FQ, three new donor-acceptor type TADF materials (TQ-oMeOTPA, TsQ-oMeOTPA and SQ-oMeOTPA) were designed by introducing 4,4'-dimethoxy triphenylamine (MeOTPA) as the donor, and introduced S atoms on the acceptors to enhance the spin-orbit coupling (SOC) and CT effects. The theoretical calculations showed that the newly introduced MeOTPA and S atom successfully enhanced the CT effect of the materials, not only shifting the luminescence peak to the deep red region but also effectively adjusting the energy level alignment of the excited state, accelerating the reverse intersystem crossing process. Finally, the organic light-emitting diodes based on SQ-oMeOTPA exhibit an external quantum efficiency of 19.1%, with an emission peak at 619 nm. This work not only expands the candidate inventory of red TADF materials, but also proves the feasibility of designing emitters by adjusting the excited state energy levels, greatly broadening the diversity of TADF emitters in design, and providing a powerful means for rapidly screening efficient emitters in the future.

Coronene: a model for ultrafast dynamics in graphene nanoflakes and PAHs.

Assuming a delta pulse excitation, quantum wavepackets are propagated on the excited state manifold in the energy range from 3.4-5.0 eV for coronene and 2.4-3.5 eV for circumcoronene to study the time evolution of the states as well as their lifetimes. The full-dimensional (102 and 210 degrees of freedom for coronene and circumcoronene respectively) non-adiabatic dynamics simulated with the ML-MCTDH method on twelve coupled singlet electronic states show that the different absorption spectra are only due to electronic delocalisation effects that change the excited state energies, but the structural dynamics in both compounds are identical. Breathing and tilting motions drive the decay dynamics of the electronic states away from the Frank-Condon region independently of the size of the aromatic system. This promising result allows the use of coronene as a model system for the dynamics of larger polycyclic aromatic hydrocarbons (PAHs) and graphene one dimensional sheets or nanoflakes.

Thermally activated delayed fluorescence emitters for efficient sensitization of europium(III).

We demonstrate for the first time a unique approach to efficiently sensitize lanthanides(III) using photosensitizer ligands that show thermally activated delayed fluorescence (TADF). TADF ligands have very small singlet (S1) and triplet (T1) excited state energy splitting and S1/T1 energy levels are in optimum energy to the acceptor level of Eu(III) to enable high energy transfer efficiency. The synthesized Eu(III) coordination polymers with TADF ligands showed bright red luminescence with an outstanding sensitization efficiency of 90-94% and Φtot of 79-85% in poly(methyl methacrylate) encapsulated films. This rational approach of efficiently sensitizing lanthanides with TADF ligands demonstrates their great potential for imaging and optical communications applications.

Precise molecular engineering for the preparation of pyridinium photosensitizers with efficient ROS generation and photothermal conversion.

Organic photosensitizers (PSs) with aggregation-induced emission properties have great development potential in the integrated application of multi-mode diagnosis and treatment of photodynamic therapy (PDT) and photothermal therapy (PTT). However, preparing high-quality PSs with both optical and biological properties, high reactive oxygen species (ROS) and photothermal conversion ability are undoubtedly a great challenge. In this work, a series of pyridinium AIE PSs modified with benzophenone have been synthesized. A wide wavelength range of fluorescent materials was obtained by changing the conjugation and donor-acceptor strength. TPAPs5 has a significant advantage over similar compounds, and we have also identified the causes of high ROS generation and high photothermal conversion in terms of natural transition orbitals, excited state energy levels, ground-excited state configuration differences and recombination energy. Interestingly, migration of target sites was also found in biological imaging experiments, which also provided ideas for the design of double-targeted fluorescent probes. Therefore, the present work proposed an effective molecular design strategy for synergistic PDT and PTT therapy.

Electric-field modulated energy transfer in phosphorescent material- and fluorescent material-codoped polymer light-emitting diodes.

The excited-state energy transfer widely exists in mixed-material systems and devices. The modulation of an electric field on the energy transfer in photoluminescence has been demonstrated. However, to date, no studies on the electric-field modulation of the excited-state energy transfer in organic optoelectronic devices have been reported. Herein, we investigate the effect of an electric field on the energy transfer in the poly(N-vinylcarbazole) (PVK) thin films doped with iridium(iii)[bis(4,6-difluorophenyl)pyridinato-N,C2']-tetrakis(1-pyrazolyl)borate (Fir6) and 5,6,11,12-tetraphenylnaphthacene (rubrene) (PVK:Fir6:rubrene) and the corresponding light-emitting diodes. Combined with the Onsager model describing electric-field enhanced exciton dissociation, we find that the electric field increases the rate of Dexter energy transfer from Fir6 to rubrene in the films and the diodes. The voltage-dependent color shift in the PVK:Fir6:rubrene light-emitting diodes can be explained by the electric-field enhanced Dexter energy transfer from Fir6 to rubrene. Our findings are important for the control of energy transfer process in organic optoelectronic devices by an electric field for desirable applications.

Magnetic field modulation of polaron relaxation coherence effects in III-V semiconductor Gaussian quantum wells

We have theoretically investigated the effects of the cyclotron frequency of magnetic field, the initial depth and the range of the asymmetrical Gaussian confinement potential on the vibrational frequency, ground state energy, excited state energy and coherence time of polaron in III-V semiconductors by using a linear combination operator and unitary transformations methods. Through numerical calculations, we find some interesting phenomena that the polaron decreases the energy level and releases the energy of a phonon to jump. From the point of view of the energy level of the polaron, which is αℏωLO energy lower than that of the electron, and the transition of the polaron to the ground state will have a change in lattice position, and the lattice relaxation phenomenon will appear. The theoretical study of the quantum coherence effect of polaron energy levels will provide guidance for the development of optoelectronic devices and the transmission of quantum information.

Excited-state normal-mode analysis: The case of porphyrins.

We systematically applied excited-state normal mode analysis to investigate and compare the relaxation and internal conversion dynamics of a free-base porphyrin (BP) with those of a novel functional porphyrin (FP) derivative. We discuss the strengths and limitations of this method and employ it to predict very different dynamical behaviors of the two compounds and to clarify the role of high reorganization energy modes in driving the system toward critical regions of the potential energy landscape. We identify the modes of vibrations along which the energy gap between two excited-state potential energy surfaces within the Q band manifold may vanish and find that the excess energy to reach this "touching" region is significantly reduced in the case of FP (0.16eV) as compared to the one calculated for BP (0.92eV). Our findings establish a link between the chemical functionalization and the electronic and vibrational structure that can be exploited to control the internal conversion pathways in a systematic way.

Cost-Effective Approach for Modeling of Multiresonant Thermally Activated Delayed Fluorescence Emitters.

Multiresonant thermally activated delayed fluorescence (MR-TADF) emitters have recently attracted great interest for application in organic light-emitting diodes due to their remarkable electroluminescent efficiency and narrow emission spectra. It is therefore essential to establish computational methodologies that can accurately model the excited states of these materials at manageable computational costs. With regard to MR-TADF design and their associated photophysics, previous works have highlighted the importance of wave function-based methods, at much higher computational costs, over the traditional time-dependent density functional theory approach. Herein, we employ two independent techniques built on different quantum mechanical frameworks, highly correlated wave function-based STEOM-DLPNO-CCSD and range-separated double hybrid density functional, TD-B2PLYP, to investigate their performance in predicting the excited state energies in MR-TADF emitters. We demonstrate a remarkable mean absolute deviation (MAD) of ∼0.06 eV in predicting ΔEST compared to experimental measurements across a large pool of chemically diverse MR-TADF molecules. Furthermore, both methods yield superior MAD in estimating S1 and T1 energies over earlier reported SCS-CC2 computed values [J. Chem. Theory Comput. 2022, 18, 4903]. The short-range charge-transfer nature of low-lying excited states and narrow fwhm values, hallmarks of this class of emitters, are precisely captured by both approaches. Finally, we show the transferability and robustness of these methods in estimating rates of radiative and nonradiative events with adequate agreement against experimental measurements. Implementing these cost-effective computational approaches is poised to streamline the identification and evaluation of potential MR-TADF emitters, significantly reducing the reliance on costly laboratory synthesis and characterization processes.

Capturing excited-state structural snapshots of evolutionary green-to-red photochromic fluorescent proteins.

Photochromic fluorescent proteins (FPs) have proved to be indispensable luminous probes for sophisticated and advanced bioimaging techniques. Among them, an interplay between photoswitching and photoconversion has only been observed in a limited subset of Kaede-like FPs that show potential for discovering the key mechanistic steps during green-to-red photoconversion. Various spectroscopic techniques including femtosecond stimulated Raman spectroscopy (FSRS), X-ray crystallography, and femtosecond transient absorption were employed on a set of five related FPs with varying photoconversion and photoswitching efficiencies. A 3-methyl-histidine chromophore derivative, incorporated through amber suppression using orthogonal aminoacyl tRNA synthetase/tRNA pairs, displays more dynamic photoswitching but greatly reduced photoconversion versus the least-evolved ancestor (LEA). Excitation-dependent measurements of the green anionic chromophore reveal that the varying photoswitching efficiencies arise from both the initial transient dynamics of the bright cis state and the final trans-like photoswitched off state, with an exocyclic bridge H-rocking motion playing an active role during the excited-state energy dissipation. This investigation establishes a close-knit feedback loop between spectroscopic characterization and protein engineering, which may be especially beneficial to develop more versatile FPs with targeted mutations and enhanced functionalities, such as photoconvertible FPs that also feature photoswitching properties.

Oscillator strengths and excited-state couplings for double excitations in time-dependent density functional theory.

Although useful to extract excitation energies of states of double-excitation character in time-dependent density functional theory that are missing in the adiabatic approximation, the frequency-dependent kernel derived earlier [Maitra et al., J. Chem. Phys. 120, 5932 (2004)] was not designed to yield oscillator strengths. These are required to fully determine linear absorption spectra, and they also impact excited-to-excited-state couplings that appear in dynamics simulations and other quadratic response properties. Here, we derive a modified non-adiabatic kernel that yields both accurate excitation energies and oscillator strengths for these states. We demonstrate its performance on a model two-electron system, the Be atom, and on excited-state transition dipoles in the LiH molecule at stretched bond-lengths, in all cases producing significant improvements over the traditional approximations.

Enhancing NIR-II Imaging and Photothermal Therapy for Improved Oral Cancer Theranostics by Combining TICT and Aggregation-Induced Emission.

In the treatment process of cancers like oral cancer, it is necessary to employ extensive surgical resection to achieve cancer eradication. However, this often results in damage to crucial functions such as chewing and speaking, leading to a poorer prognosis and a reduced quality of life. To address this issue, a multifunctional theranostic agent named MBPN-T-BTD has been developed by precisely modulating the excitation state energy distribution in the radiative/nonradiative decay pathways using the characteristics of twisted intramolecular charge transfer and aggregation-induced emission. This agent outperforms clinically utilized indocyanine green (ICG) in various aspects, including the second near-infrared window (NIR-II, 1000-1700 nm) fluorescence (FL) and photothermal conversion efficiency (PCE). Its nanoparticle form (BTB NPs) can be effectively used for high-contrast delineation of lymph node mapping and tongue and floor of mouth cancers using NIR-II FL, enabling surgeons to achieve more precise and thorough tumor clearance. For tumors located in close proximity to vital organs such as the tongue, the exceptional PCE (71.96%) of BTB NPs allows for targeted photothermal ablation with minimal damage to peripheral healthy tissues. This contribution provides a safer and more effective paradigm for minimally invasive or noninvasive treatment of oral cancer, ensuring the preservation of normal organ functions and showing potential for improving the overall prognosis and quality of life for cancer patients.

Configuration-mediated excited-state energy dissipation in metal-bridged dimeric D-A fluorophores for enhanced photothermal therapy

Photothermal agents (PTAs) based on donor (D)-acceptor (A) NIR fluorophores show great promise in photothermal therapy due to their accessible molecular engineering to mediate excitation energy for high photothermal conversion. Except for molecular structural modification of D-A fluorophores, intermolecular arrangement in space greatly influences their excitation energy dissipation as well. But how to mediate their intermolecular arrangement is still challenging. Here we control the intermolecular orientation of chromophores via metal coordination to form Pt-bridged dimeric D-A fluorophores with different geometries. The formed configuration isomers show different intermolecular exciton coupling behaviors involving charge transfer (CT) evolution and internally limited molecular rotation, which greatly affect excited-energy dissipation. Compared with folded configuration with intense NIR emission (quantum yields (QYs) = 15.62 %), linear configuration favors non-radiative decays with low QYs (6.99 %) but enhanced photothermal conversion efficiency (PCE = 41.57 %). The self-assembled nanoparticles combining Pt-bridged dimeric D-A fluorophores with DSPE-PEG2000-RGD reveal superior photothermal therapeutic features with desirable biosafety. This research provides a new designing concept to mediate excited-state energy dissipation pathways at a sub-nano level for enhanced photothermal conversion. Statement of significanceD-A fluorophores as photothermal agents attract great attention in photothermal therapy due to their accessible molecular engineering. Besides molecular engineering of D-A fluorophores, the intermolecular packing manner is proven to greatly affect their excitation energy dissipation. But how to control intermolecular arrangement is still challenging. Here we control the intermolecular orientation of chromophores via metal coordination to form Pt-bridged dimeric D-A fluorophores with different geometries. Compared to the folded configuration, linear configuration facilitates charge transfer (CT) evolution and molecular rotation, which promotes non-radiative decays of excited energy for enhanced photothermal therapy.

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.

Antimony Doping Enabled Photoluminescence Quantum Yield Enhancement in 0D Inorganic Bismuth Halide Crystals.

Owing to the exterior self-trapped excitons (STEs) with adjustable fluorescence beams, low-dimensional ns2-metal halides have recently received considerable attention in solid-state light-emitting applications. However, the photoluminescence (PL) mechanism in metal halides remains a major challenge in achieving high efficiency and controllable PL properties because the excited-state energy of ns2 conformational ions varies inhomogeneously with their coordination environments. Here, a novel zero-dimensional (0D) lead-free bismuth-based Rb3BiCl6·0.5H2O crystal was reported as a pristine crystal to modulate the optical properties. By doping Sb3+ ions with 5s2 electrons into Rb3BiCl6·0.5H2O crystals, bright orange emission at room temperature was obtained with a photoluminescence quantum yield of 39.7%. Optical characterizations and theoretical studies show that the Sb3+ doping can suppress the strong exciton-phonon coupling, optimize the electronic energy band structure, improve the thermal activation energy, soften the structural lattice of the host crystals, deepen the STE states, and ultimately lead to strong photoluminescence. This work manifests a fruitful manipulation in ripening bismuth-based halides with high-efficiency PL properties, and the PL enhancement mechanisms will guide future research in the exploration of emerging luminescent materials.

Ab initio calculations for well deformed nuclei: 40Mg and 42Si

We performed ab initio valence-space in-medium similarity renormalization group calculations based on chiral nucleon-nucleon and three-nucleon interactions to study the neutron-rich nuclei around N=28, where the experimental and theoretical evidence point to a rapid transition from spherical to rotational regimes. First, the rotational spectra of 40Mg, 42Si, and 44S are established theoretically, anchored by the calculated E2 transition strength. The results suggest that 40Mg and 42Si exhibit large deformations. After that, the erosion of the N=28 shell closure, especially the evolutions of shape deformation and the emergence of shape coexistence, are discussed in N=28 even-even isotones ranging from 40Mg to 48Ca. Finally, the shell evolution of N=28 in Mg and Si chains is discussed based on the experimental and predicted excitation energies of low-lying states. The results from our ab initio calculations align well with available experimental data, furnishing essential insights into the structure of neutron-rich nuclei, particularly deformations in the vicinity of 40Mg and 42Si.

Robust Optical Detection of Ga3+ by a Rhodamine- and Coumarin-Based Proficient Probe: Theoretical Investigations and Biological Applications.

The present investigation highlights a rhodamine-B- and coumarin-based efficient probe that selectively detects Ga3+ over other metal ions. The active pocket of the ligand for trapping the metal ions and the binding stoichiometry of its Ga3+ complex were discovered by single-crystal X-ray diffraction (SC-XRD) analysis. This binding stoichiometry was further confirmed in the solution state by mass spectrometry and Job's plot. The detection limit was found to be at the nanomolar level. Pyrophosphate being a well-known quencher could easily quench the fluorescence intensity of the RC in the presence of Ga3+ and reversibly recognize Ga3+ in the solution. The spiro ring opening of the ligand after Ga3+ insertion is proposed to be the principal mechanism for the turn-on fluorescence response. This ring opening was confirmed by SC-XRD data and nuclear magnetic resonance (NMR) titration experiments. Both ground- and excited-state calculations of the ligand and complex have been carried out to obtain information about their energy levels and to obtain the theoretical electronic spectra. Furthermore, the live-cell imaging of the probe only and the probe after the addition of Ga3+ have been carried out in HaCaT cells and satisfactory responses were observed. Interestingly, with the help of this probe, Ga3+ can be tracked inside the intracellular organelle such as lysosomes along with other regions of the cell. The article highlights a rhodamine-coumarin-based probe for the detection of Ga3+ over other metal ions with a nanomolar level detection limit. Structural characterization of the ligand and its Ga3+ complex was investigated by SC-XRD. Density functional theory (DFT) and time-dependent DFT (TD-DFT) studies were carried out to explore the excited-state energies and electronic spectra. The application of the probe for the detection of Ga3+ in live cells has been explored, and positive responses were observed.

Broadband 2.85 μm Luminescence Properties of Er3+/Dy3+ Co-Doped Fluorotellurite Glass

TeO2-BaF2-Er2O3-Dy2O3 laser glasses were prepared using the melt-quenching method. The bound water that can capture the excited state energy was reduced by physical and chemical methods. We did not observe a significant Er3+ emission peak at 2.7 μm in fluorescence spectra, which may be due to the efficient energy transfer process (ET2). Meanwhile, we found a broadband gain span of approximately 400 nm in fluorescence spectra at the 2.85 μm band, attributed to the ‘vector summation’ of the energy level radiation transition and the change of the glass network. Subsequently, we explored the structural properties of the glass. The results indicated that the Gaussian peak located at 250 cm−1 drifts toward 370 cm−1, which may be caused by the fracture or recombination of Te-O-Te and a decrease in the bridge oxygen content with the increasing concentration of Er2O3. The topology cage structure around the luminescence center of rare earth ions is changed and the stability of the optically active center is enhanced, finally contributing to the enhancement of luminescence. Meanwhile, the maximum σemi and gain coefficient of Dy3+ reach up to 7.22 × 10−21 cm2 and 7.37 cm−1, respectively. The comprehensive results show that the fluorotellurite glass designed in this study is expected to be a gain medium for mid-infrared lasers in remote sensing monitoring, military, and other fields.

Theoretical Study on the Optoelectronic Properties of Merocyanine-Dyes.

Merocyanines, as prototypes of highly polar π-conjugated molecules, have been intensively investigated for their self-assembly and optoelectronic properties, both experimentally and theoretically. However, an accurate description of their structural and electronic properties remains challenging for quantum-chemical methods. We assessed several theoretical approaches, TD-DFT, GW-BSE, STEOM-DLPNO-CCSD, and CASSCF/NEVPT2-FIC for their reliability in reproducing optoelectronic properties of a series of donor/acceptor (D/A) merocyanines, focusing on the first excitation energy. Additionally, we tested an all-electron perturbative method based on time-dependent coupled-perturbed density functional theory, denoted as TDCP-DFT. Particular focus was set on direct and indirect solvent effects, which affect excited-state energies by electrostatic interaction and molecular geometry. The molecular configuration space was sampled at the semiempirical tight-binding level. Our results corroborate previous investigations, showing that the S0 - S1 excitation energy strongly depends on the merocyanine molecular structure and the dielectric constant of the solvent. We found significant effects of the polar solution environment on the geometry of the merocyanines, which strongly affect the calculated excitation energies. Taking these effects into account, the best agreement between calculated and measured excitation energies was obtained with TDCP-DFT and GW-BSE. We also calculated excitation energies of molecular crystals at the TDCP-DFT level and compared the results to the corresponding monomers.

Near-infrared OLEDs with high radiance of ∼105 mW Sr−1 m−2 for single-wavelength oxygen saturation detection

Real-time in-home monitoring oxygen saturation (SpO2) is of great significance for early diagnosis and treatment of severe COVID-19, however, which should be based on multi-wavelength technology and complicated equipment. Herein, as a proof of concept, 740 nm is chosen as singlet light source for single-wavelength SpO2 detection, since absorbance differences between oxyhemoglobin (HbO2) and other interferences are the most rational. To controllably optimize excited-state characteristics of a near-infrared (NIR) thermally activated delayed fluorescence (TADF) emitters, an “extra conjugation” method is demonstrated by CNQP-TPA, whose 2,3-dicyanoquinoxaline phenanthroline (CNQP) acceptor forms strong intramolecular hydrogen bonds with two phenyls of triphenylamine (TPA) donors, which not only reduce excited-state relaxation-induced energy lose, but also provide more space for accurate modulation of intermolecular charge transfer (CT) interactions. As consequence, at the suitable doping concentration, CNQP-TPA endowed its device with a high radiance reaching ∼105 mW Sr−1 m−2 and desired electroluminescence peak at 744 nm. This device is further used as light source to detect SpO2 variation under single-wavelength mode. These results indicate the potential of NIR TADF materials and devices for in-home SpO2 monitoring and pre-diagnosis and prevention of severe COVID-19.