Quenching singlet oxygen via intersystem crossing for a stable Li-O2 battery.

Aprotic Li-O2 batteries are a promising energy storage technology, however severe side reactions during cycles lead to their poor rechargeability. Herein, highly reactive singlet oxygen (1O2) is revealed to generate in both the discharging and charging processes and is deterimental to battery stability. Electron-rich triphenylamine (TPA) is demonstrated as an effective quencher in the electrolyte to mitigate 1O2 and its associated parasitic reactions, which has the tertiary amine and phenyl groups to manifest excellent electrochemical stability and chemical reversibility. It reacts with electrophilic 1O2 to form a singlet complex during cycles, and it then quickly transforms to a triplet complex through nonradiative intersystem crossing (ISC). This efficiently accelerates the conversion of 1O2 to the ground-state triplet oxygen to eliminate its derived side reactions, and the regeneration of TPA. These enable the Li-O2 battery with obviously reduced overvoltages and prolonged lifetime for over 310 cycles when coupled with a RuO2 catalyst. This work highlights the ISC mechanism to quench 1O2 in Li-O2 battery.

Ab initio molecular dynamics study of intersystem crossing dynamics for MH2 (M = Si, Ge, Sn, Pb) on spin-pure and spin-mixed potential energy surfaces.

Recently, surface-hopping ab initio molecular dynamics (SH-AIMD) simulations have come to be used to discuss the mechanisms and dynamics of excited-state chemical reactions, including internal conversion and intersystem crossing. In dynamics simulations involving intersystem crossing, there are two potential energy surfaces (PESs) governing the motion of nuclei: PES in a spin-pure state and PES in a spin-mixed state. The former gives wrong results for molecular systems with large spin-orbit coupling (SOC), while the latter requires a potential gradient that includes a change in SOC at each point, making the computational cost very high. In this study, we systematically investigate the extent to which the magnitude of SOC affects the results of the spin-pure state-based dynamics simulations for the hydride MH2 (M = Si, Ge, Sn, Pb) by performing SH-AIMD simulations based on spin-pure and spin-mixed states. It is clearly shown that spin-mixed state PESs are indispensable for the dynamics simulation of intersystem crossing in systems containing elements Sn and Pb from the fifth period onward. Furthermore, in addition to the widely used Tully's fewest switches (TFS) algorithm, the Zhu-Nakamura (ZN) global switching algorithm, which is computationally less expensive, is applied to SH for comparison. The results from TFS- and ZN-SH-AIMD methods are in qualitative agreement, suggesting that the less expensive ZN-SH-AIMD can be successfully utilized to investigate the dynamics of photochemical reactions based on quantum chemical calculations.

Glutathione-responsive Aggregation-induced Emission Photosensitizers for Enhanced Photodynamic Therapy of Lung Cancer.

Lung cancer, a highly prevalent and lethal form of cancer, is often associated with oxidative stress. Photodynamic therapy (PDT) has emerged as a promising alternative therapeutic tool in cancer treatments, but its efficacy is closely correlated to the photosensitizers generating reactive oxygen species (ROS) and the antioxidant capacity of tumor cells. In particular, glutathione (GSH) can reduce the ROS and thus compromise PDT efficacy. In this study, a GSH-responsive near-infrared photosensitizer (TBPPN) based on aggregation-induced emission for real-time monitoring of GSH levels and enhanced PDT for lung cancer treatment is developed. The strategic design of TBPPN, consisting of a donor-acceptor structure and incorporation of dinitrobenzene, enables dual functionality by not only the fluorescence being activated by GSH but also depleting GSH to enhance the cytotoxic effect of PDT. TBPPN demonstrates synergistic PDT efficacy in vitro against A549 lung cancer cells by specifically targeting different cellular compartments and depleting intracellular GSH. In vivo studies further confirm that TBPPN can effectively inhibit tumor growth in a mouse model with lung cancer, highlighting its potential as an integrated agent for the diagnosis and treatment of lung cancer. This approach enhances the effectiveness of PDT for lung cancer and deserves further exploration of its potential for clinical application.

Reproducible and High-Performance WOLEDs Based on Independent High-Efficiency Triplet Harvesting of Yellow Hot-Exciton ESIPT and Blue TADF Emitters.

Hot exciton organic light-emitting diode (OLED) emitters can balance the high performance of a device and reduce efficiency roll-off by fast reverse intersystem crossing from high-lying triplets (hRISC). In this study, an excited-state intramolecular proton transfer (ESIPT) fluorophore of 2-(benzo[d]thiazol-2-yl)-4-(pyren-1-yl)phenol (PyHBT) with the typical characteristic properties of a hot exciton is developed. With high efficiency of utilization of the exciton (91%), its yellow OLED exhibited high external quantum efficiency (EQE) of 5.6%, current efficiency (CE) of 16.8 cd A-1 , and power efficiency (PE) of 17.3 lm W-1 . The performance of the yellow emissive "hot exciton" ESIPT fluorophores is among the highest recorded. Due to the large Stokes shift of the ESIPT emitter, non-energy-transferred high-performance white OLEDs (WOLEDs) are developed, which are reproducible and highly efficient. This is possible because of the independent harvesting of most of the triplets in both complementary-color emitters without the interference of energy transfer. The PyHBT-based WOLEDs exhibit a maximum EQE of 14.3% and CE of 41.1 cd A-1 , which facilitates the high-yield mass production of inexpensive WOLEDs.

Room Temperature Phosphorescence in Crystalline Iodinated Eumelanin Monomer.

We report the room temperature phosphorescence upon iodination on a crystalline eumelanin monomer with shielded hydroxyl moieties, ethyl 5,6-dimethoxyindole-2-carboxylate (DMICE). Ultrafast intersystem crossing (ISC) is observed in the iodinated (IDMICE) as well as brominated (BDMICE) analogues of the eumelanin monomer derivative in solution. The triplet quantum yields (φT) and intersystem crossing rates (kISC) of the halogenated eumelanin derivatives are φ T B D M I C E ${{\phi{} }_{T}^{BDMICE}}$ =25.4±1.1 %; k I S C B D M I C E ${{k}_{ISC}^{BDMICE}}$ =1.95×109 s-1 and φ T I D M I C E ${{\phi{} }_{T}^{IDMICE}}$ =59.1±1.6 %; k I S C I D M I C E = ${{k}_{ISC}^{IDMICE}=}$ 1.36×1010 s-1, as monitored using transient absorption spectroscopy. Theoretical calculations based on nuclear ensemble method reveal that computed kISC and spin-orbit coupling matrix elements for eumelanin derivatives are larger for IDMICE relative to BDMICE. The halogen and π-π interactions, with distinct excitonic coupling and higher ISC rate promote phosphorescence in IDMICE molecular crystals. Accessing triplet excited states and resultant photoluminescence through structural modification of eumelanin scaffolds paves way for exploring the versatility of eumelanin-inspired molecules as bio-functional materials.

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.

Structural and Electronic Factors Controlling the Efficiency and Rate of Intersystem Crossing to the Triplet State in Thiophene Polycyclic Derivatives.

Thiophene polycyclic derivatives are widely used in organic light-emitting diodes, photovoltaics, and medicinal chemistry applications. Understanding the electronic and structural factors controlling their intersystem crossing rates is paramount for these applications to be successful. This study investigates the photophysical, electronic structure, and excited state dynamics of 1,2-benzodiphenylene sulfide, benzo[b]naphtho[1,2-d]thiophene, and benzo[b]naphtho[2,3-d]thiophene in polar aprotic and non-polar solvents. Steady-state absorption and emission spectroscopy, femtosecond transient absorption spectroscopy, and DFT and TD-DFT calculations are employed. Low fluorescence quantum yields of 1.2 to 2.7% are measured in acetonitrile and cyclohexene, evidencing that the primary relaxation pathways in these thiophene derivatives are nonradiative. Linear interpolation of internal coordinates calculations predict that an S-C bond elongation reaction coordinate facilitates the efficient intersystem crossing to the T1 state. Excitation of 1,2-benzodiphenylene sulfide and benzo[b]naphtho[1,2-d]thiophene at 350 nm or benzo[b]naphtho[2,3-d]thiophene at 365 nm, populates the lowest-energy 1ππ* state, which relaxes to the 1ππ* minimum in tens of picoseconds or intersystem crosses to the triplet manifold in ca. 500 ps to 1.1 ns depending on the position at which the benzene rings are added. Excitation at 266 nm does not affect the intersystem crossing rates. Laser photodegradation experiments demonstrate that the thiophene polycyclic derivatives are highly photostable.

Multiple Pathways in the Triplet States Population for a Naphthalenediimide-C60 Dyad.

The link of an antenna dye with an electron spin converter, in this case naphthalenediimide and C60, produces a system with a rich photophysics including the detection of more than one triplet state on the long timescale (tens of µs). Beside the use of optical spectroscopies in the ns and in the fs time scale, we used time-resolved Electron Paramagnetic Resonance (TREPR) to study the system evolution following photoexcitation. TREPR keeps track of the formation path of the triplet states through specific spin polarization patterns observed in the spectra. The flexibility of the linker and solvent polarity play a role in favouring either electron transfer or energy transfer processes.

Thio and Seleno-Psoralens as Efficient Triplet Harvesting Photosensitizers for Photodynamic Therapy.

The Psoralen (Pso) molecule finds extensive applications in photo-chemotherapy, courtesy of its triplet state forming ability. Sulfur and selenium replacement of exocyclic carbonyl oxygen of organic chromophores foster efficient triplet harvesting with near unity triplet quantum yield. These triplet-forming photosensitizers are useful in Photodynamic Therapy (PDT) applications for selective apoptosis of cancer cells. In this work, we have critically assessed the effect of the sulfur and selenium substitution at the exocyclic carbonyl (TPso and SePso, respectively) and endocyclic oxygen positions of Psoralen. It resulted in a significant redshifted absorption spectrum to access the PDT therapeutic window with increased oscillator strength. The reduction in singlet-triplet energy gap and enhancement in the spin-orbit coupling values increase the number of intersystem crossing (ISC) pathways to the triplet manifold, which shortens the ISC lifetime from 10-5 s for Pso to 10-8 s for TPso and 10-9 s for SePso. The intramolecular photo-induced electron transfer process, a competitive pathway to ISC, is also considerably curbed by exocyclic functionalizations. In addition, a maximum of 115 GM of two-photon absorption (2PA) with IR absorption (660-1050 nm) confirms that the Psoralen skeleton can be effectively tweaked via single chalcogen atom replacement to design a suitable PDT photosensitizer.

Driving Triplet State Population in Benzothioxanthene Imide Dyes: Let's twist!

Controlling the formation of photoexcited triplet states is critical for many (photo)chemical and physical applications. Here, we demonstrate that a permanent out-of-plane distortion of the benzothioxanthene imide (BTI) dye promotes intersystem crossing by increasing spin-orbit coupling. This manipulation was achieved through a subtle chemical modification, specifically the bay-area methylation. Consequently, this simple yet efficient approach expands the catalog of known molecular engineering strategies for synthesizing heavy atom-free, dual redox-active, yet still emissive and synthetically accessible photosensitizers.

Near-IR-Absorbing Bis-Donor Functionalized Aza-BODIPY Derivatives: Synthesis and Photophysical Study by Using Transient Optical Spectroscopy.

A series of near-IR absorbing 2,6-diarylated BF2-chelated aza-boron-dipyrromethenes (aza-BDPs) derivatives bearing different electron donors (benzene, naphthalene, phenanthrene, phenothiazine and carbazole) were designed and synthesized. The effect of different electron donor substitutions on the photophysical properties was studied by steady-state UV-vis absorption and fluorescence spectra, electrochemical, time-resolved nanosecond transient absorption (ns-TA) spectroscopy and theoretical computations. The UV-vis absorption spectra of AzaBDP-PTZ and AzaBDP-CAR (λabs=710 nm in toluene) showed a bathochromic absorption profile compared with the reference AzaBDP-Ph (λabs=685 nm in toluene), indicating the non-negligible electronic interaction at the ground state between donor and acceptor moieties. Moreover, the fluorescence is almost completely quenched for AzaBDP-PTZ/AzaBDP-CAR (fluorescence quantum yield, ΦF=0.2-0.7 % in toluene) as compared with the AzaBDP-Ph (ΦF=27 % in toluene). However, the apparent intersystem crossing ability of these compounds is poor, based on the singlet oxygen quantum yield (ΦΔ=0.3-1.5 %). The ns-TA spectral study showed typical Bodipy localized triplet state transient features, short-lived excited triplet state for AzaBDP-Ph (τT=53.2 µs) versus significantly long-lived triplet state for AzaBDP-CAR (τT=114 µs) was observed under deaerated experimental conditions. These triplet state lifetimes are much longer than that obtained with diiodoAzaBDP (intramolecular heavy atom effect, τT=1.5~7.2 µs). These information are useful for molecular structure design of triplet photosensitizers, for which longer triplet state lifetimes are usually desired. Theoretical computations displayed that the triplet state is mainly localized on the AzaBDP core, moreover, it was found that the HOMO/LUMO energy gap decreased after introducing donor moieties to the skeleton as compared with the reference.

Creating Efficient Red Thermally Activated Delayed Fluorescence Materials with Cyano-Substituted 11,12-Diphenyldipyrido[3,2-a:2',3'-c]phenazine Acceptors.

Red luminescent materials are essential components for full color display and white lightening based on organic light-emitting diode (OLED) technology, but the extension of emission color towards red or deep red region generally leads to decreased photoluminescence and electroluminescence efficiencies. Herein, we wish to report two new luminescent molecules (2CNDPBPPr-TPA and 4CNDPBPPr-TPA) consisting of cyano-substituted 11,12-diphenyldipyrido[3,2-a:2',3'-c]phenazine acceptors and triphenylamine donors. As the increase of cyano substituents, the emission wavelength is greatly red-shifted and the reverse intersystem crossing process is promoted, resulting in strong red delayed fluorescence. Meanwhile, due to the formation of intramolecular hydrogen bonds, the molecular structures become rigidified and planarized, which brings about large horizontal dipole ratios. As a result, 2CNDPBPPr-TPA and 4CNDPBPPr-TPA can perform as emitters efficiently in OLEDs, furnishing excellent external quantum efficiencies of 28.8 % at 616 nm and 20.2 % at 648 nm, which are significantly improved in comparison with that of the control molecule without cyano substituents. The findings in this work demonstrate that the introduction of cyano substituents to the acceptors of delayed fluorescence molecules could be a facile and effective approach to explore high-efficiency red or deep red delayed fluorescence materials.

Orthogonal Geometry Enhancing the Intersystem Crossing and Photosensitive Efficiency of Spiro Organoboron Compounds.

Based on the reported spiro organoboron compounds (PS1 and PS2 as potent 1O2 sensitizers), several new organoboron molecules (PS4-PS9) were constructed through structural modification, and their low-lying excited states and photophysical properties have been explored by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. The predicted effective intersystem crossing (ISC) processes arise from the S1→T2 transition for PS4-PS6 and the S1→T4 transition for PS1, and corresponding KISC rate constants reach the order of magnitude of 109 (s-1). The organoboron compounds with a (N, N) chelate acceptor are predicted to exhibit relatively higher ISC efficiency than those bearing a (N, O) acceptor, and the planar C3NBN ring and the orthogonal configuration between the donor and acceptor moieties are responsible for the ISC rate enhancement. Importantly, the geometric features of the lowest singlet excited state (S1) for these compounds play a decisive role in their photosensitive efficiency. The present results provide a basis for better understanding of the photosensitivity of these spiro organoboron compounds and the structural modification effect.

Density Functional Theory Calculations on Fluorescence-Enhanced Mechanisms of the Optical Sensor for Zinc Ions, ADPA.

N-(9-anthracenylmethyl)-N-(2-pyridinylmethyl)-2-pyridinemethanamine (ADPA) as a specific ion sensor for Zn2+ has been widely applied. Although the photo-induced electron transfer (PET) mechanism was proposed previously, its fluorescence-enhanced effect still remains somewhat ambiguous, according to unknown influences of non-radiative energy decay pathways, such as intersystem crossing and internal conversion. Herein, a thorough study using density functional theory has been performed for low-lying electronic states of the ADPA monomer and hydrated ADPA-Zn2+ complex. Based on interfragment charge transfer analyses, we quantitatively calculated the amount of transferred electrons in the monomer and complex, providing solid evidences for the PET mechanism and in line with the conclusion of frontier molecular orbital analyses. Moreover, the ISC process of S1→T2 was confirmed to play a considerable role in the excitation energy relaxation process of the ADPA monomer, but this influence was significantly suppressed in the hydrated ADPA-Zn2+ complex. These results provide additional clues for the design of new metal ion-specific fluorescence probes.

Studies on Fluorescence Quenching, Decay Rate Parameters, Dipole Moment, Rotational Diffusion of 3-(benzo[d]thiazol-2-yl)-7-(diethylamino)-2H-chromen-2-one Laser Dye in Excited Singlet State: Temperature Effect.

The effect of temperature on the absorption and emission characteristics of 3-(benzo[d]thiazol-2-yl)-7-(diethylamino)-2H-chromen-2-one (3BT7D2H-one) laser dye in glycerol solvent has been studied by the steady-state method. Fluorescence intensity decreases with an increase in temperature and shifts towards a shorter wavelength. Parameters like fluorescence lifetime, rate constants, activation energy, and dipole moment (using the thermochromic method) are determined experimentally. Also, the temperature effect on rotational diffusion of 3BT7D2H-one laser dye is studied and also estimated theoretical and experimental hydrodynamic volumes.

Tuning the Electronic and Optical Properties of Phenoxaborin Based Thermally Activated Delayed Fluorescent Materials: A DFT Study.

The electronic and optoelectronic properties of molecules constituted by benzene as linker, phenoxaborin as acceptor coupled with different types of donor moieties are investigated using the density functional theoretical method. The energy gap between the first excited singlet and triplet states (ΔEST) of the designed molecules (1-9) is found to be less than 0.5 eV suggesting them as ideal candidates for thermally activated delayed fluorescence (TADF) emitters. The analysis of frontier molecular orbitals of the molecules revealed a minimum spatial overlap between highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) in favor of the small values of ΔEST. Among the molecules studied, the one in which dihydrophenazine acts as the donor has the lowest value of ΔEST. All designed molecules are good electron transporters. The non-linear optical properties of the molecules are also examined.

Novel Photocatalyst Based on Through-Space Charge Transfer Induced Intersystem Crossing Enables Rapid and Efficient Polymerization Under Low-Power Excitation Light.

Currently, most photoredox catalysis polymerization systems are limited by high excitation power, long polymerization time, or the requirement of electron donors due to the precise design of efficient photocatalysts still poses a great challenge. Herein, we propose a new approach: the creation of efficient photocatalysts having low ground state oxidation potentials and high excited state energy levels, along with through-space charge transfer (TSCT) induced intersystem crossing (ISC) properties. A cabazole-naphthalimide (NI) dyad (NI-1) characterized by long triplet excited state lifetime (τT=62 µs), satisfactory ISC efficiency (ΦΔ=54.3 %) and powerful reduction capacity [Singlet: E1/2 (PC+1/*PC)=-1.93 eV, Triplet: E1/2 (PC+1/*PC)=-0.84 eV] was obtained. An efficient and rapid polymerization (83 % conversion of 1 mM monomer in 30 s) was observed under the conditions of without electron donor, low excitation power (10 mW cm-2) and low catalyst (NI-1) loading (<50 µM). In contrast, the conversion rate was lower at 29 % when the reference catalyst (NI-4) was used for photopolymerization under the same conditions, demonstrating the advantage of the TSCT photocatalyst. Finally, the TSCT material was used as a photocatalyst in practical lithography for the first time, achieving pattern resolutions of up to 10 µm.

Tuning the Absorption, Fluorescence, Intramolecular Charge Transfer, and Intersystem Crossing in Spiro[fluorene]acridinone.

In this work, we prepared a series of electron donor-acceptor systems based on spiro[fluorene-9,7'-dibenzo[c,h]acridine]-5'-one (SFDBAO). Our SFDBAOs consist of orthogonally positioned fluorenes and aromatic ketones. By fine-tuning the substitution of electron-donating pyrenes, the complex interplay among different excited-state decay channels and the overall impact of solvents on these decay channels were uncovered. Placing pyrene, for example, at the aromatic ketones resulted in a profound solvatochromism in the form of a bright charge-transfer (CT) emission spanning from yellow to red-NIR. In contrast, a dark non-emissive CT was noted upon pyrene substitution at the fluorenes. In apolar solvents, efficient triplet-excited state generation was observed for all SFDBAOs. Either charge transfer was concluded to mediate the intersystem crossing (ISC) in the case of pyrene substitution or the El-Sayed rule was applicable when lacking pyrene substitution as in the case of SFABAO. In polar solvents, charge separation is the sole decay upon pyrene substitution. Moreover, competition between ISC and CT lowered the triplet-excited state generation in SFDBAO.

Appending Coronene Diimide with Carbon Nanohoops Allows for Rapid Intersystem Crossing in Neat Film.

The development of innovative triplet materials plays a significant role in various applications. Although effective tuning of triplet formation by intersystem crossing (ISC) has been well established in solution, the modulation of ISC processes in the solid state remains a challenge due to the presence of other exciton decay channels through intermolecular interactions. The cyclic structure of cycloparaphenylenes (CPPs) offers a unique platform to tune the intermolecular packing, which leads to controllable exciton dynamics in the solid state. Herein, by integrating an electron deficient coronene diimide (CDI) unit into the CPP framework, a donor-acceptor type of conjugated macrocycle (CDI-CPP) featuring intramolecular charge-transfer (CT) interaction was designed and synthesized. Effective intermolecular CT interaction resulting from a slipped herringbone packing was confirmed by X-ray crystallography. Transient spectroscopy studies showed that CDI-CPP undergoes ISC in both solution and the film state, with triplet generation time constants of 4.5 ns and 238 ps, respectively. The rapid triplet formation through ISC in the film state can be ascribed to the cooperation between intra- and intermolecular charge-transfer interactions. Our results highlight that intermolecular CT interaction has a pronounced effect on the ISC process in the solid state, and shed light on the use of the characteristic structure of CPPs to manipulate intermolecular CT interactions.

Di-benzoquinone Cyclopentadithiophene Diradicaloids Show Spin-States Optical Transitions and Anomalous NIR Emission.

We have prepared a series of bis(semiquinone) compounds with dithiophene bridges of different length that evolve from closed-shell to full diradical character on the basis of the narrow singlet-triplet energy gaps which allows the triplet population at 298 K for the longer compound. The medium size compound has a variety of photonic properties with absorptions and emission in the true NIR region mediated by a unique case of antikasha emission. A whole set of optical absorption and emission steady state and pico-second transient absorption spectroscopies together with vibrational spectroscopies, spectroelectrochemistry and theoretical calculations have been carried our and subsequently interpreted.