Conversion Of Excitons Research Articles

A critical overview of rate models for the determination of the rate constants associated with thermally activated delayed fluorescence

Thermally activated delayed fluorescence (TADF) is a photophysical phenomenon that involves electronically coupled singlet and triplet excited states. Materials exhibiting TADF have most prominently been employed in organic light-emitting diodes (OLEDs). Electroluminescent devices with TADF emitters are capable of converting up to 100% of the excitons generated to light. The microsecond long delayed lifetimes and the sensitivity of the emission to the environment have been exploited in sensing, imaging, and photocatalysis applications. TADF relies on there being energetically similar singlet and triplet excited states, which enables not only intersystem crossing (ISC) but also the endothermic conversion of triplet excitons to singlet excitons via reverse intersystem crossing (RISC). The coupling of the singlet and triplet excited states leads to a biexponential decay of the emission that is observed in the transient photoluminescence (PL) of the material. It means that although emission is from the singlet, at long time its dynamics are controlled by the triplet population via the RISC process. This review provides an overview of the methods used in the literature to analyze the PL decay of TADF compounds and to infer the rate constants that govern all facets of the TADF process. While the photophysics of TADF is often analyzed using transient PL, most applications of TADF emitters occur in a steady-state regime facilitated by constant exciton generation and recombination. Thus, this review also discusses the link between parameters of the kinetics and the performance of TADF OLEDs.

Boosting External Quantum Efficiency to 12.0 % of an Ultraviolet OLED by Engineering the Horizontal Dipole Orientation of a Hot Exciton Emitter

AbstractCurrently, much research effort has been devoted to improving the exciton utilization efficiency and narrowing the emission spectra of ultraviolet (UV) fluorophores for organic light‐emitting diode (OLED) applications, while almost no attention has been paid to optimizing their light out‐coupling efficiency. Here, we developed a linear donor‐acceptor‐donor (D–A–D) triad, namely CDFDB, which possesses high‐lying reverse intersystem crossing (hRISC) property. Thanks to its integrated narrowband UV photoluminescence (PL) (λPL: 397 nm; FWHM: 48 nm), moderate PL quantum yield (ϕPL: 72 %, Tol), good triplet hot exciton (HE) conversion capability, and large horizontal dipole ratio (Θ//: 92 %), the OLEDs based on CDFDB not only can emit UV electroluminescence with relatively good color purity (λEL: 398 nm; CIEx,y: 0.161, 0.040), but also show a record maximum external quantum efficiency (EQEmax) of 12.0 %. This study highlights the important role of horizontal dipole orientation engineering in the molecular design of HE UV‐OLED fluorophores.

Boosting External Quantum Efficiency to 12.0 % of an Ultraviolet OLED by Engineering the Horizontal Dipole Orientation of a Hot Exciton Emitter.

Currently, much research effort has been devoted to improving the exciton utilization efficiency and narrowing the emission spectra of ultraviolet (UV) fluorophores for organic light-emitting diode (OLED) applications, while almost no attention has been paid to optimizing their light out-coupling efficiency. Here, we developed a linear donor-acceptor-donor (D-A-D) triad, namely CDFDB, which possesses high-lying reverse intersystem crossing (hRISC) property. Thanks to its integrated narrowband UV photoluminescence (PL) (λPL: 397 nm; FWHM: 48 nm), moderate PL quantum yield (ϕPL: 72 %, Tol), good triplet hot exciton (HE) conversion capability, and large horizontal dipole ratio (Θ//: 92 %), the OLEDs based on CDFDB not only can emit UV electroluminescence with relatively good color purity (λEL: 398 nm; CIEx,y: 0.161, 0.040), but also show a record maximum external quantum efficiency (EQEmax) of 12.0 %. This study highlights the important role of horizontal dipole orientation engineering in the molecular design of HE UV-OLED fluorophores.

Polymeric triazine/heptazine imide heterostructures enable photocatalytic O2reduction to H2O2

Heptazine-based carbon nitrides are a class of transition metal free semiconductors, which are extensively studied in various photocatalytic processes. The localized nature of the excitons, incomplete exciton conversion into the charge-separated state and the recombination of the charge carriers are the factors that limit performance of the pristine heptazine-based carbon nitrides. Herein, we design heterojunctions composed of poly(triazine imide) intercalated by LiCl and poly(heptazine imide) phases. The donor-acceptor character of the heterojunctions improves the charge separation yield. The heterojunction with the optimal composition of the phases shows an apparent quantum yield of H2O2 formation of 14 % at 365 nm and 7 % at 465 nm, while the H2O2 production rate reaches 7.8 mol L−1 gphotocatalyst−1 h−1 (39 mmol L−1 h−1 produced by 5 mg of photocatalyst) in batch and 15.9 mol kgphotocatalyst−1 h−1 in flow using a packed-bed photoreactor. The heterojunction undergoes photocharging under anaerobic conditions. The charges stored in the material after irradiation enable O2 reduction to H2O2 in the dark with the rate 367 µmol gphotocatalyst−1 h−1 (1.8 µmol h−1 stored in 5 mg of photocatalyst).

Pivotal role of water vapor–mediated defect engineering on SrTiO3 nanofiber toward efficient photocatalytic water splitting

The oxygen vacancies (OVs) have played key roles as either charge carrier traps for inhibiting recombination or directly as active sites for photocatalytic redox reactions. In this study, the population and types of oxygen vacancies within the electrospun SrTiO3 nanofibers were modulated through water vapor and air atmosphere annealing respectively. Combining the distinctive 1D nanofibrous structure with optimized OVs, the water vapor–mediated OVs-rich SrTiO3 nanofibers achieved a significant enhancement in specific surface area and porosity, effectively suppressing the recombination of photogenerated carriers. The OVs can effectively promote the conversion of photon excitons into charge carriers, accelerate the carrier separation, and facilitate surface redox reaction. The optimized water vapor–mediated STO-W-700 exhibited abundant active sites and rapid surface charge separation/migration across the nanofibers, leading to an exceptional hydrogen production performance of 296.82 μmolg/h. During the photocatalytic process, the OVs act synergistically with nearby metal sites to optimize the adsorption energy of reactants. This work not only provides an effective pathway for manipulating oxygen vacancies through water vapor–mediated defect engineering strategy, but also reveals a new water splitting mechanism, laying the foundation for further research and development of efficient solar energy conversion technologies.

Lateral epitaxial growth of two-dimensional organic heterostructures.

Two-dimensional organic lateral heterostructures (2D OLHs) are attractive for the fabrication of functional materials. However, it is difficult to control the nucleation, growth and orientation of two distinct components. Here we report the combination of two methods-liquid-phase growth and vapour-phase growth-to synthesize 2D OLHs from perylene and a perylenecarboxaldehyde derivative, with a lateral size of ~20 μm and a tunable thickness ranging from 20 to 400 nm. The screw dislocation growth behaviour of the 2D crystals shows the spiral arrangement of atoms within the crystal lattice, which avoids volume expansion and contraction of OLH, thereby minimizing lateral connection defects. Selective control of the nucleation and sequential growth of 2D crystals leads to structural inversion of the 2D OLHs by the vapour-phase growth method. The resulting OLHs show good light-transport capabilities and tunable spatial exciton conversion, useful for photonic applications. This synthetic strategy can be extended to other families of organic polycyclic aromatic hydrocarbons, as demonstrated with other pyrene and perylene derivatives.

Organic Bilayer Heterostructures with Built-In Exciton Conversion for 2D Photonic Encryption.

Organic multilayer heterostructures with accurate spatial organization demonstrate strong light-matter interaction from excitonic responses and efficient carrier transfer across heterojunction interfaces, which are considered as promising candidates toward advanced optoelectronics. However, the precise regulation of the heterojunction surface area for finely adjusting exciton conversion and energy transfer is still formidable. Herein, organic bilayer heterostructures (OBHs) with controlled face-to-face heterojunction via a stepwise seeded growth strategy, which is favorable for efficient exciton propagation and conversion of optical interconnects are designed and synthesized. Notably, the relative position and overlap length ratio of component microwires (LDSA /LBPEA = 0.39-1.15) in OBHs are accurately regulated by modulating the crystallization time of seeded crystals, resulting into a tailored heterojunction surface area (R = Loverlap /LBPEA = 37.6%-65.3%). These as-prepared OBHs present the excitation position-dependent waveguide behaviors for optical outcoupling characteristics with tunable emission colors and intensities, which are applied into two-dimensional (2D) photonic barcodes. This strategy opens a versatile avenue to purposely design OBHs with tailored heterojunctions for efficient energy transfer and exciton conversion, facilitating the application possibilities of advanced integrated optoelectronics.

Observation of ultrafast interfacial Meitner-Auger energy transfer in a Van der Waals heterostructure

Atomically thin layered van der Waals heterostructures feature exotic and emergent optoelectronic properties. With growing interest in these novel quantum materials, the microscopic understanding of fundamental interfacial coupling mechanisms is of capital importance. Here, using multidimensional photoemission spectroscopy, we provide a layer- and momentum-resolved view on ultrafast interlayer electron and energy transfer in a monolayer-WSe2/graphene heterostructure. Depending on the nature of the optically prepared state, we find the different dominating transfer mechanisms: while electron injection from graphene to WSe2 is observed after photoexcitation of quasi-free hot carriers in the graphene layer, we establish an interfacial Meitner-Auger energy transfer process following the excitation of excitons in WSe2. By analysing the time-energy-momentum distributions of excited-state carriers with a rate-equation model, we distinguish these two types of interfacial dynamics and identify the ultrafast conversion of excitons in WSe2 to valence band transitions in graphene. Microscopic calculations find interfacial dipole-monopole coupling underlying the Meitner-Auger energy transfer to dominate over conventional Förster- and Dexter-type interactions, in agreement with the experimental observations. The energy transfer mechanism revealed here might enable new hot-carrier-based device concepts with van der Waals heterostructures.

Effect of Conductive Polymers PEDOT:PSS on Exciton Recombination and Conversion in Doped-Type BioLEDs.

Although the effect of the conductive polymers PEDOT:PSS on the electroluminescence performance of doped-type organic light-emitting diodes (OLEDs) has been studied, the process of PEDOT:PSS regulation of exciton recombination region and concentration within the deoxyribonucleic acid (DNA)-based doped-type BioLEDs is still obscure. In this study, we fabricated Bio-devices with and without PEDOT:PSS using varying spin-coating speeds of PEDOT:PSS. The Alq3:Rubrene-based BioLEDs achieve higher luminance (44,010 cd/m2) and higher luminance efficiency (8.1 cd/A), which are increased by 186% and 478%, respectively, compared to the reference BioLEDs without PEDOT:PSS. Similarly, the maximum luminance and efficiency of blue TCTA:TPBi exciplex-type BioLEDs are increased by 224% and 464%. In particular, our findings reveal that with an increasing thickness of PEDOT:PSS, the region of exciton recombination shifts towards the interface between the emitting layer (EML) and the hole transport layer (HTL). Meanwhile, the concentration of singlet exciton (S1,Rub) and triplet exciton (T1,Rub) increases, and the triplet-triplet annihilation (TTA) process is enhanced, resulting in the enhanced luminescence and efficiency of the devices. Accordingly, we provide a possible idea for achieving high performance doped-type BioLEDs by adding conductive polymers PEDOT:PSS, and revealing the effect of exciton recombination and conversion in BioLEDs given different PEDOT:PSS thicknesses.

Overcoming the Limitation of Spin Statistics in Organic Light Emitting Diodes (OLEDs): Hot Exciton Mechanism and Its Characterization.

Triplet harvesting processes are essential for enhancing efficiencies of fluorescent organic light-emitting diodes. Besides more conventional thermally activated delayed fluorescence and triplet-triplet annihilation, the hot exciton mechanism has been recently noticed because it helps reduce the efficiency roll-off and improve device stability. Hot exciton materials enable the conversion of triplet excitons to singlet ones via reverse inter-system crossing from high-lying triplet states and thereby the depopulation of long-lived triplet excitons that are prone to chemical and/or efficiency degradation. Although their anti-Kasha characteristics have not been clearly explained, numerous molecules with behaviors assigned to the hot exciton mechanism have been reported. Indeed, the related developments appear to have just passed the stage of infancy now, and there will likely be more roles that computational elucidations can play. With this perspective in mind, we review some selected experimental studies on the mechanism and the related designs and then on computational studies. On the computational side, we examine what has been found and what is still missing with regard to properly understanding this interesting mechanism. We further discuss potential future points of computational interests toward aiming for eventually presenting in silico design guides.

Derivatives of 2-Pyridone Exhibiting Hot-Exciton TADF for Sky-Blue and White OLEDs.

Development of emissive materials for utilization in organic light-emitting diodes (OLEDs) remains a highly relevant research field. One of the most important aspects in the development of efficient emitters for OLEDs is the efficiency of triplet-to-singlet exciton conversion. There are many concepts proposed for the transformation of triplet excitons to singlet excitons, among which thermally activated delayed fluorescence (TADF) is the most efficient and widespread. One of the variations of the TADF concept is the hot exciton approach according to which the process of exciton relaxation into the lowest energy electronic state (internal conversion as usual) is slower than intersystem crossing between high-lying singlets and triplets. In this paper, we present the donor-acceptor materials based on 2-pyridone acceptor coupled to the different donor moieties through the phenyl linker demonstrating good performance as components of sky-blue, green-yellow, and white OLEDs. Despite relatively low photoluminescence quantum yields, the compound containing 9,9-dimethyl-9,10-dihydroacridine donor demonstrated very good efficiency in sky-blue OLED with the single emissive layer, which showed an external quantum efficiency (EQE) of 3.7%. It also forms a green-yellow-emitting exciplex with 4,4',4″-tris[phenyl(m-tolyl)amino]triphenylamine. The corresponding OLED showed an EQE of 6.9%. The white OLED combining both exciplex and single emitter layers demonstrated an EQE of 9.8% together with excellent current and power efficiencies of 16.1 cd A-1 and 6.9 lm W-1, respectively. Quantum-chemical calculations together with the analysis of photoluminescence decay curves confirm the ability of all of the studied compounds to exhibit TADF through the hot exciton pathway, but the limiting factor reducing the efficiency of OLEDs is the low photoluminescence quantum yields caused mainly by nonradiative intersystem crossing dominating over the radiative fluorescence pathway.

Boosting internal quantum efficiency via ultrafast triplet transfer to 2H-MoTe2 film.

Organic systems often allow to create two triplet spin states (triplet excitons) by converting an initially excited singlet spin state (a singlet exciton). An ideally designed organic/inorganic heterostructure could reach the photovoltaic energy harvest over the Shockley-Queisser (S-Q) limit because of the efficient conversion of triplet excitons into charge carriers. Here, we demonstrate the molybdenum ditelluride (MoTe2)/pentacene heterostructure to boost the carrier density via efficient triplet transfer from pentacene to MoTe2 using ultrafast transient absorption spectroscopy. We observe carrier multiplication by nearly four times by doubling carriers in MoTe2 via the inverse Auger process and subsequently doubling carriers via triplet extraction from pentacene. We also verify efficient energy conversion by doubling the photocurrent in the MoTe2/pentacene film. This puts a step forward to enhancing photovoltaic conversion efficiency beyond the S-Q limit in the organic/inorganic heterostructures.

Single-Atom Engineering of Covalent Organic Framework for Photocatalytic H2 Production Coupled with Benzylamine Oxidation.

In photocatalysis, reducing the exciton binding energy and boosting the conversion of excitons into free charge carriers are vital to enhance photocatalytic activity. This work presents a facile strategy of engineering Pt single atoms on a 2D hydrazone-based covalent organic framework (TCOF) to promote H2 production coupled with selective oxidation of benzylamine. The optimised TCOF-Pt SA photocatalyst with 3 wt% Pt single atom exhibited superior performance to TCOF and TCOF-supported Pt nanoparticle catalysts. The production rates of H2 and N-benzylidenebenzylamine over TCOF-Pt SA3 are 12.6 and 10.9 times higher than those over TCOF, respectively. Empirical characterisation and theoretical simulation showed that the atomically dispersed Pt is stabilised on the TCOF support through the coordinated N1 -Pt-C2 sites, thereby induing the local polarization and improving the dielectric constant to reach the low exciton binding energy. These phenomena led to the promotion of exciton dissociation into electrons and holes and the acceleration of the separation and transport of photoexcited charge carriers from bulk to the surface. This work provides new insights into the regulation of exciton effect for the design of advanced polymer photocatalysts.

Design of Intramolecular Dihedral Angle between Electronic Donor and Acceptor in Thermally Activated Delayed Fluorescence Molecules.

In order to improve the exciton utilization efficiency (ηexc) of organic light-emitting materials, we addressed the ideal donor-acceptor dihedral angle (θD-A) in the TADF molecule by striking a balance between two photophysical processes. One is the conversion of triplet excitons into singlet excitons, and the other is the radiative process from a low-lying excited state to the ground state. Using a combination of first-principles calculations and molecular dynamics simulations, we investigated the impact of θD-A on the splitting energy and spin-orbit coupling between singlet and triplet excitons as well as the transition dipole moment for carbazole benzonitrile (CzBN) derivatives. By comparison with the reverse intersystem crossing rate (krISC), fluorescence emission rate (kr), and ηexc, we proposed a potential highest ηexc (of 94.4%) with the ideal θD-A of 77° for blue light CzBN derivatives; the calculated results have a good agreement with experimental measurement. The structure-efficiency physical connection between the molecular structure (θD-A) and efficiency provided an ideal parameter for a potential candidate for blue TADF-OLED materials.

Robustness of Momentum-Indirect Interlayer Excitons in MoS2/WSe2 Heterostructure against Charge Carrier Doping

Monolayer transition-metal dichalcogenide (TMD) semiconductors exhibit strong excitonic effects and hold promise for optical and optoelectronic applications. Yet, electron doping of TMDs leads to the conversion of neutral excitons into negative trions, which recombine predominantly non-radiatively at room temperature. As a result, the photoluminescence (PL) intensity is quenched. Here we study the optical and electronic properties of a MoS2/WSe2 heterostructure as a function of chemical doping by Cs atoms performed under ultra-high vacuum conditions. By PL measurements we identify two interlayer excitons and assign them to the momentum-indirect Q-Gamma and K-Gamma transitions. The energies of these excitons are in a very good agreement with ab initio calculations. We find that the Q-Gamma interlayer exciton is robust to the electron doping and is present at room temperature even at a high charge carrier concentration. Submicrometer angle-resolved photoemission spectroscopy (micro-ARPES) reveals charge transfer from deposited Cs adatoms to both the upper MoS2 and the lower WSe2 monolayer without changing the band alignment. This leads to a small (10 meV) energy shift of interlayer excitons. Robustness of the momentum-indirect interlayer exciton to charge doping opens up an opportunity of using TMD heterostructures in light-emitting devices that can work at room temperature at high densities of charge carriers.

Tunable interlayer excitons and switchable interlayer trions via dynamic near-field cavity

Emerging photo-induced excitonic processes in transition metal dichalcogenide (TMD) heterobilayers, e.g., interplay of intra- and inter-layer excitons and conversion of excitons to trions, allow new opportunities for ultrathin hybrid photonic devices. However, with the associated large degree of spatial heterogeneity, understanding and controlling their complex competing interactions in TMD heterobilayers at the nanoscale remains a challenge. Here, we present an all-round dynamic control of interlayer-excitons and -trions in a WSe2/Mo0.5 W0.5 Se2 heterobilayer using multifunctional tip-enhanced photoluminescence (TEPL) spectroscopy with <20 nm spatial resolution. Specifically, we demonstrate the bandgap tunable interlayer excitons and the dynamic interconversion between interlayer-trions and -excitons, through the combinational tip-induced engineering of GPa-scale pressure and plasmonic hot electron injection, with simultaneous spectroscopic TEPL measurements. This unique nano-opto-electro-mechanical control approach provides new strategies for developing versatile nano-excitonic/trionic devices using TMD heterobilayers.

Multiple resonance induced thermally activated delayed fluorescence: effect of chemical modification

Thermally activated delayed fluorescence (TADF) is the internal conversion of triplet excitons into singlet excitons via reverse intersystem crossing (RISC). It improves the efficiency of organic light-emitting diodes (OLED) by enabling the harvesting of nonradiative triplet excitons. Multiple resonance (MR) induced TADF chromophores exhibit an additional advantage of high color purity due to their rigid conformation. However, owing to the strict design rules there is a limited number of known MR-TADF chromophores. For applications in full-color high-resolution OLED displays, it is desirable to extend the variety of available chromophores and their color range. We computationally explore the effect of chemical modification on the properties of the MR-TADF chromophore quinolino[3,2,1-de]acridine-5,9-dione (QAD). QAD derivatives are evaluated based on several metrics: The formation energy is associated with the ease of synthesis; The spatial distribution of the frontier orbitals indicates whether a compound remains an MR-TADF chromophore or turns into a donor–acceptor TADF chromophore; The change of the singlet excitation energy compared to the parent compound corresponds to the change in color; The energy difference between the lowest singlet and triplet states corresponds to the barrier to RISC; The reorganization energy is associated with the color purity. Based on these metrics, QAD-6CN is predicted to be a promising MR-TADF chromophore with a cyan hue. This demonstrates that computer simulations may aid the design of new MR-TADF chromophores by chemical modification.

Enhancement of Valley Polarization in Monolayer WSe2 Coupled with Microsphere‐Cavity‐Array

AbstractMonolayer transition metal dichalcogenides (ML‐TMDCs) possess degenerate levels with antiparallel spins in K and K′ valleys, providing the intrinsic valley polarization, which attracts great interest for potential applications on quantum information technology and on‐chip nanophotonics. Unfortunately, it is difficult to distinguish the degree of valley polarization (DoP) near room temperature due to the intensive phonon‐assisted intervalley scattering and the long‐range electron‐hole exchange interaction in ML‐TMDCs, limiting their practical applications. In this study, a novel design is proposed for great promotion of DoP in ML‐WSe2 with a microsphere cavity array, introducing Purcell effect and nanofocusing effect into the system. The radiative decay rate is dramatically enhanced owing to Purcell effect in microcavity in weak coupling regime, thus locking more polarized excitons in the corresponding valley under certain circularly‐polarized pumping. In addition, the nanofocusing effect contributes to increasing the number of charged excitons by suppressing the bright to dark exciton conversion. The present work achieves a great DoP of ML‐WSe2 with a simple configuration and promises broad applications from valleytronic devices to chiral optics in the future.

Room temperature synthesis of double perovskite Cs2AlBiCl6 for photovoltaic applications

Toxicity and stability issue in lead halide inorganic perovskite nanomaterial can be solved with the help of lead free double perovskite (DP) nanocrystals (NCs). Herein, we have synthesized a new halide double perovskite material Cs2AlBiCl6 for the first time and explored its structural and optical properties which further shows remarkable similarities to lead induced compounds. Also, in this article we have demonstrated the solar cell device based on the synthesized material showing power conversion efficiency of 1.965% which is remarkable and comparable to the single perovskites based solar cell devices. This material is showing promising absorbance phenomenon with a direct and indirect band gap of 3.23 eV and 2.63 eV respectively with excellent stability under ambient condition. The formation of synthesized double perovskite phase has been confirmed using X-ray powder diffraction (XRD) which results into a high purity and good crystallinity of the material. The temperature dependent photoluminescence (TDPL) phenomenon from 19 K to 300 K has been recorded to understand the luminescent behavior of the material. An excellent photoluminescence has been observed due to self-trapped exciton (STE) emission attributed to the distortion in the lattice. A decrease in intensity with increase in temperature has been observed due to conversion of excitons into free carriers with the help of thermal energy. This novel experimental study suggest the utility of Cs2AlBiCl6 as a stable and green alternatives for optoelectronic applications and provide a broad and undiscovered compositional space for finding promising semiconducting materials for optoelectronic and photovoltaic devices applications.

Unraveling the Efficiency of Thioxanthone Based Triplet Sensitizers: A Detailed Theoretical Study.

Photochemical activation by triplet photosensitizers is highly expedient for a green focus society. In this work, we have theoretically probed excited state characteristics of thioxanthone and its derivatives for their triplet harvesting efficiency using density functional theory (DFT) and time-dependent density functional theory (TDDFT). Absorption and triplet energies corroborate well with the available experimental data. Our results predict that both the S1 and T1 states are π-π* in nature, which renders a high oscillator strength for S0 to S1 transition. Major triplet exciton conversion occurs through intersystem crossing (ISC) channel between the S1 (1 π-π* ) and high energy 3 n- π* state. Apart from that, there is both radiative and non-radiative channel from S1 to S0 , which competes with the ISC channel and reduces the triplet harvesting efficiency. For thioxanthones with -OMe (Me=Methyl) or -F substitution at 2 or 2' positions, the ISC channel is not energetically feasible, causing sluggish intersystem crossing quantum yield (ΦISC ). For unsubstituted thioxanthone and for isopropyl substitution at 2' position, the S1 -T1 gap is slightly positive ( ), rendering a lower triplet harvesting efficiency. For systems with -OMe or -F substitution at 3 or 3' position of thioxanthone, because of buried π state and high energy π* state, the S1 -3 nπ* gap becomes negative. This leads to a high ΦISC (>0.9), which is key to being an effective photocatalyst.