Local Excited State Research Articles

Modulation of the photobehavior of gefitinib and its phenolic metabolites by human transport proteins.

The photobiological damage that certain drugs or their metabolites can photosensitize in proteins is generally associated with the nature of the excited species that are generated upon interaction with UVA light. In this regard, the photoinduced damage of the anticancer drug gefitinib (GFT) and its two main photoactive metabolites GFT-M1 and GFT-M2 in cellular milieu was recently investigated. With this background, the photophysical properties of both the drug and its metabolites have now been studied in the presence of the two main transport proteins of human plasma, i.e., serum albumin (HSA) and α1-acid glycoprotein (HAG) upon UVA light excitation. In general, the observed photobehavior was strongly affected by the confined environment provided by the protein. Thus, GFT-M1 (which exhibits the highest phototoxicity) showed the highest fluorescence yield arising from long-lived HSA-bound phenolate-like excited species. Conversely, locally excited (LE) states were formed within HAG, resulting in lower fluorescence yields. The reserve was true for GFT-M2, which despite being also a phenol, led mainly to formation of LE states within HSA, and phenolate-like species (with a minor contribution of LE) inside HAG. Finally, the parent drug GFT, which is known to form LE states within HSA, exhibited a parallel behavior in the two proteins. In addition, determination of the association constants by both absorption and emission spectroscopy revealed that the two metabolites bind stronger to HSA than the parent drug, whereas smaller differences were observed for HAG. This was further confirmed by studying the competing interactions between GFT or its metabolites with the two proteins using fluorescence measurements. These above experimental findings were satisfactorily correlated with the results obtained by means of molecular dynamics (MD) simulations, which revealed the high affinity binding sites, the strength of interactions and the involved amino acid residues. In general, the differences observed in the photobehavior of the drug and its two photoactive metabolites in protein media are consistent with their relative photosensitizing potentials.

Symmetry-breaking charge separation in a null-excitonic 3-dimensional rigid nonconjugated trimer.

Photoinduced symmetry-breaking charge separation (SB-CS) has been extensively observed in various oligomers and aggregates, which holds great potential for robust artificial solar energy conversion systems. It attaches great importance to the precise manipulation of interchromophore electronic coupling in realizing efficient SB-CS. The emerging studies on SB-CS suggested that it could be realized in null-excitonic aggregates, and a long-lived SB-CS state was observed, which offers an advanced platform and has gathered immense attention in the SB-CS field. Here, we unveiled the null-exciton coupling induced ultrafast SB-CS in a rigid polycyclic aromatic hydrocarbon framework, triperyleno[3,3,3]propellane triimides (TPPTI), in which three chromophores were attached through a nonconjugated bridge. Through a combination of theoretical calculations and steady-state absorption results, we demonstrated that this nonconjugated TPPTI possesses negligible exciton coupling. Increased solvent polarity was found to significantly enhance state mixing between local excited and charge transfer states. Using transient absorption spectroscopy, ultrafast SB-CS was observed in highly polar dimethylformamide, facilitated by a selective hole-transfer coupling and a favorable charge separation free energy (ΔGCS). Additionally, the rate ratio between SB-CS and charge recombination was at least high to 1800 in dimethylformamide. This investigation provides profound insights into the role of null-exciton coupling in dominating ultrafast SB-CS in multichromophoric systems.

Theoretical investigation of distal charge separation in a perylenediimide trimer

An exciton–phonon (ex–ph) model based on our recently developed block interaction product basis framework is introduced to simulate the distal charge separation (CS) process in aggregated perylenediimide (PDI) trimer incorporating the quantum dynamic method, i.e., the time-dependent density matrix renormalization group. The electronic Hamiltonian in the ex–ph model is represented by nine constructed diabatic states, which include three local excited (LE) states and six charge transfer (CT) states from both the neighboring and distal chromophores. These diabatic states are automatically generated from the direct products of the leading localized neutral or ionic states of each chromophore’s reduced density matrix, which are obtained from ab initio quantum chemical calculation of the subsystem consisting of the targeted chromophore and its nearest neighbors, thus considering the interaction of the adjacent environment. In order to quantum-dynamically simulate the distal CS process with massive coupled vibrational modes in molecular aggregates, we used our recently proposed hierarchical mapping approach to renormalize these modes and truncate those vibrational modes that are not effectively coupled with electronic states accordingly. The simulation result demonstrates that the formation of the distal CS process undergoes an intermediate state of adjacent CT, i.e., starts from the LE states, passes through an adjacent CT state to generate the intermediates (∼200 fs), and then formalizes the targeted distal CS via further charge transference (∼1 ps). This finding agrees well with the results observed in the experiment, indicating that our scheme is capable of quantitatively investigating the CS process in a realistic aggregated PDI trimer and can also be potentially applied to exploring CS and other photoinduced processes in larger systems.

Exciplex Formation by Complexation of an Electron-Accepting Guest in an Electron-Donating Pillar[5]arene Host Liquid.

We present a novel system, a liquid-state pillar[5]arene decorated with tri(ethylene oxide) chains, that brings electron-donor and electron-acceptor molecules into proximity for efficient exciplex formation. The electron-accepting guests exhibit a blue-purple emission from a localized excited state upon excitation in common solvents. However, directly dissolving the guests in the electron-donating pillar[5]arene liquid (a bulk system) results in visible green emission from the formed exciplexes. In the bulk system, the guest molecules are always surrounded by excess pillar[5]arene molecules, resulting in the formation of mainly inclusion-type exciplexes. In the bulk system, energy migration occurs between the pillar[5]arene molecules. Excitation of the pillar[5]arenes results in a more intense green exciplex emission than that observed upon direct excitation of the guests. In summary, the pillar[5]arene liquid is a novel system for achieving efficient exciplex formation and energy migration that is different from typical solvent and solid systems.

Derivatives of Phenyl Pyrimidine and of the Different Donor Moieties as Emitters for OLEDs.

Two derivatives of phenyl pyrimidine as acceptor unit and triphenylamino or 4,4'-dimethoxytriphenylamino donor groups were designed and synthesized as emitters for organic light-emitting diodes (OLEDs) aiming to utilize triplet excitons in the electroluminescence. Thermogravimetric analysis revealed high thermal stability of the compounds with 5% weight loss temperatures of 397 and 438 °C. The theoretical estimations and photophysical data show the contributions of local excited and charge transfer states into emission. The addition of the methoxy groups led to the significant improvement of hole-transporting properties and the bathochromic shift of the emission from blue to green-blue spectral diapason. It is shown that mixing of the compounds with the organic host results in facilitation of the delayed emission. The singlet-triplet energy splitting was found to be too big for the thermally activated delayed fluorescence. No thermal activation of the long-lived emission was detected. No experimental evidence for triplet-triplet annihilation and room temperature phosphorescence were detected making the hot exciton mechanism the most probable one. The OLEDs based on the compounds reached the maximum external quantum efficiency of up to 10.6%.

Room-Temperature Phosphorescence Materials Featuring Triplet Hybrid Local Charge Transfer Emission.

Room-temperature phosphorescence materials have found important applications in dissolved oxygen sensing, temperature monitoring, anticounterfeiting, etc., because of their prolonged phosphorescence lifetime. However, the known systems mainly utilize the triplet local excited state emission, which is generally less sensitive to microenvironment perturbation. In this work, we designed a series of 4-phenyl-1,8-naphthalimide (NMI) derivatives containing different numbers of carbazole (Cz) units (denoted as NMI-Cz, NMI-2Cz, and NMI-3Cz). Steady state and time-resolved spectroscopy studies determined that the compounds undergo intramolecular through-space charge transfer in solution, yielding a triplet hybrid local charge transfer state. Room-temperature phosphorescence emission was observed in compound-doped poly(methyl methacrylate) thin films upon ammonia treatment. Interestingly, emission from different films exhibited different persistence times. We believe a film-based, time-resolved luminescent ammonia sensor could be developed by making a device of the emissive films as fabricated.

Ultrafast and Multichannel Generation of the Triplet State in DNA-Intercalated Gilvocarcin V for an Enhanced Photoaddition Reaction.

Gilvocarcin V (GV) is a natural antibiotic exhibiting excellent antitumor activities and remarkably low toxicity in near-ultraviolet or visible light-dependent treatment. Notwithstanding, the [2 + 2] cycloaddition reaction between GV and thymine has been proven to be the key for its function in photodynamic therapy, and crucial mechanistic details about such a reaction are poorly understood. In this study, the electronic relaxation pathways and photoaddition reaction are characterized by femto- to nanosecond time-resolved spectroscopy combined with quantum chemical calculation. Our results reveal that ultrafast intersystem crossing (<3 ps) leads to the population of a local triplet excited state in DNA-intercalated GV. Such a state can further induce the formation of a biradical state, which is identified as the important reactive precursor for photoaddition between GV and thymine. The overall photoaddition quantum efficiency is determined to be 11.57 ± 1.0%. These results are essential to the elucidation of the DNA photoaddition mechanism of C-aryl glycoside-based artificial photocytotoxic agents and could help further development of those medicines.

Powders to Thin Films: Advances in Conjugated Microporous Polymer Chemical Sensors.

Chemical sensing of harmful species released either from natural or anthropogenic activities is critical to ensuring human safety and health. Over the last decade, conjugated microporous polymers (CMPs) have been proven to be potential sensor materials with the possibility of realizing sensing devices for practical applications. CMPs found to be unique among other porous materials such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) due to their high chemical/thermal stability, high surface area, microporosity, efficient host-guest interactions with the analyte, efficient exciton migration along the π-conjugated chains, and tailorable structure to target specific analytes. Several CMP-based optical, electrochemical, colorimetric, and ratiometric sensors with excellent selectivity and sensing performancewere reported. This review comprehensively discusses the advances in CMP chemical sensors (powders and thin films) in the detection of nitroaromatic explosives, chemical warfare agents, anions, metal ions, biomolecules, iodine, and volatile organic compounds (VOCs), with simultaneous delineation of design strategy principles guiding the selectivity and sensitivity of CMP. Preceding this, various photophysical mechanisms responsible for chemical sensing are discussed in detail for convenience. Finally, future challenges to be addressed in the field of CMP chemical sensors are discussed.

Visible Light Induced Exciton Dynamics and trans-to-cis Isomerization in Azobenzene Aggregates: Insights from Surface Hopping/Semiempirical Configuration Interaction Molecular Dynamics Simulations.

Assemblies of photochromic molecules feature exciton states, which govern photochemical and photophysical processes in multichromophoric systems. Understanding the photoinduced dynamics of the assemblies requires nonadiabatic treatment involving multiple exciton states and numerous nuclear degrees of freedom, thus posing a challenge for simulations. In this work, we address this challenge for aggregates of azobenzene, a prototypical molecular switch, performing on-the-fly surface hopping calculations combined with semiempirical configuration interaction electronic structure and augmented with transition density matrix analysis to characterize exciton evolution. Specifically, we consider excitation of azobenzene tetramers in the nπ* absorption band located in the visible (blue) part of the electromagnetic spectrum, thus extending our recent work on dynamics after ππ* excitation corresponding to the ultraviolet region [Titov, J. Phys. Chem. C2023, 127, 13678-13688]. We find that the nπ* excitons, which are initially strongly localized by ground-state conformational disorder, undergo further (very strong) localization during short-time photodynamics. This excited-state localization process is extremely ultrafast, occurring within the first 10 fs of photodynamics. We observe virtually no exciton transfer of the localized excitons in the nπ* manifold. However, the transfer may occur via secondary pathways involving ππ* states or the ground state. Moreover, we find that the nπ* quantum yields of the trans-to-cis isomerization are reduced in the aggregated state.

Exploring the Early Time Behavior of the Excited States of an Archetype Thermally Activated Delayed Fluorescence Molecule.

Optical pump-probe techniques allow for an in-depth study of dark excited states. Here, we utilize them to map and gain insights into the excited states involved in the thermally activated delayed fluorescence (TADF) mechanism of a benchmark TADF emitter DMAC-TRZ. The results identify different electronic excited states involved in the key TADF transitions and their nature by combining pump-probe and photoluminescence measurements. The photoinduced absorption signals are highly dependent on polarity, affecting the transition oscillator strength but not their relative energy positions. In methylcyclohexane, a strong and vibronically structured local triplet excited state absorption (3LE → 3LEn) is observed, which is quenched in higher polarity solvents as 3CT becomes the lowest triplet state. Furthermore, ultrafast transient absorption (fsTA) confirms the presence of two stable conformers of DMAC-TRZ: (1) quasi-axial (QA) interconverting within 20 ps into (2) quasi-equatorial (QE) in the excited state. Moreover, fsTA highlights how sensitive excited state couplings are to the environment and the molecular conformation.

Charge‐Transfer Modulation of Emissivity in Polarized Diketopyrrolopyrroles

AbstractStrongly polarized donor‐acceptor‐donor′ diketopyrrolopyrroles, differing in the type of key donor moiety, were designed and synthesized to examine how this affects the non‐radiative decay. Dyes possessing less electron‐rich N‐carbazolyl substituents are characterized by strong yellow emission from a locally excited (LE) state, whereas replacing this donor with more electron‐rich N‐phenothiazinyl substituent changes the relative position of charge‐transfer (CT) and LE states, leading to weaker, reddish‐orange fluorescence. As a result, there is solvent‐dependent charge‐transfer emission shifted to as far as 700 nm. The opening of the intersystem crossing channel to the triplet state possessing CT character is the most likely cause of the fluorescence quantum yield variation in some cases. These results reveal that the fate of molecules in their excited state can be fine‐tuned by very small structural changes.

A computational investigation of twelve phenylurea herbicides including photoexcitation and structural relaxation

Phenylurea herbicides are widely used to control unwanted plant growth, but can linger in the environment. Photodegradation is a key mechanism by which these compounds can be transformed. This paper investigates the direct photoabsorption and relaxation of twelve phenylurea compounds (chlorbromuron, chlortoluron, diuron, fenuron, fluometuron, isoproturon, linuron, methiuron, metobromuron, metoxuron, monolinuron, monuron) using density functional theory. Ground state structures are optimized at the B3LYP-D3/def2-SVP level of theory and excited states are computed using CAM-B3LYP-D3/def2-SVPD. These molecules are found to be mostly planar and structurally similar in the ground state, with the exception of methiuron which has a significant distortion. The vertical excitation energies are affected by the presence of halogen substituents, and trends in the relaxation of these states are observed. Specifically, halogenated compounds generally have a local excited state minimum corresponding to a stretched carbon-halogen bond, phenylureas containing a methoxy group on the nitrogen have a local minimum corresponding to a twisted urea group and/or a minimum corresponding to the breaking of the nitrogen–oxygen bond between the urea and the methoxy group. The results are discussed in the context of known photodegradation mechanisms for this class of compounds.

Ortho-Carborane Decorated Multi-Resonance TADF Emitters: Preserving Local Excited State and High Efficiency in OLEDs.

A novel class of o-carboranyl luminophores, 2CB-BuDABNA (1) and 3CB-BuDABNA (2) is reported, in which o-carborane moieties are incorporated at the periphery of the B,N-doped multi-resonance thermally activated delayed fluorescence (MR-TADF) core. Both compounds maintain the inherent local emission characteristics of their MR-emitting core, exhibiting intense MR-TADF with high photoluminescence quantum yields in toluene and rigid states. In contrast, the presence of the dark lowest-energy charge transfer state, induced by cage rotation in THF, is suggested to be responsible for emission quenching in a polar solvent. Despite the different arrangement of the cage on the DABNA core, both 1 and 2 show red-shifted emissions compared to the parent compound BuDABNA (3). By utilizing 1 as the emitter, high-efficiency blue organic light-emitting diodes (OLEDs) are achieved with a remarkable maximum external quantum efficiency of 25%, representing the highest reported efficiency for OLEDs employing an o-carboranyl luminophore as the emitter.

Shedding light on thermally-activated delayed fluorescence.

Thermally activated delayed fluorescence (TADF) is a hot research topic in view of its impressive applications in a wide variety of fields from organic LEDs to photodynamic therapy and metal-free photocatalysis. TADF is a rare and fragile phenomenon that requires a delicate equilibrium between tiny singlet-triplet gaps, sizable spin-orbit couplings, conformational flexibility and a balanced contribution of charge transfer and local excited states. To make the picture more complex, this precarious equilibrium is non-trivially affected by the interaction of the TADF dye with its local environment. The concurrent optimization of the dye and of the embedding medium is therefore of paramount importance to boost practical applications of TADF. Towards this aim, refined theoretical and computational approaches must be cleverly exploited, paying attention to the reliability of adopted approximations. In this perspective, we will address some of the most important issues in the field. Specifically, we will critically review theoretical and computational approaches to TADF rates, highlighting the limits of widespread approaches. Environmental effects on the TADF photophysics are discussed in detail, focusing on the major role played by dielectric and conformational disorder in liquid solutions and amorphous matrices.

Study of two-photon absorption and excited-state dynamics of coumarin derivatives: the effect of monomeric and dimeric structures.

Intramolecular charge transfer (ICT) and π-electron delocalization are two key factors affecting the nonlinear optical absorption of organic molecules. To clarify the different influences of ICT and π-electron delocalization on two-photon absorption (TPA) and excited-state absorption (ESA), monomeric coumarin C1 and dimeric coumarin C2 are synthesized and studied. Transient absorption spectroscopy (TAS) analysis of these coumarin derivatives in solvents of varying polarities describes the polarity-dependent excited-state dynamics and reveals the ESA signals of the charge transfer state (CTS) and local excited state (LES) with different spectral features. Femtosecond broadband Z-scan experiments indicate that dimeric coumarin C2 has a more significant TPA response than monomeric coumarin C1 in the near-infrared region. Natural transition orbital (NTO) analysis further theoretically characterizes the electron transition feature induced by TPA. Our results reveal that the TPA of these coumarin derivatives can be significantly enhanced by expanding π-electron delocalization, but their ESA is mainly dominated by ICT performance. This study indicates that coumarin derivatives will exhibit extremely broad application prospects in the field of ultrafast optical limiting (OL) through reasonable molecular design.

Ultrafast excited state relaxation dynamics of pyran-based D-π-A systems: solvent polarity controls the triplet state.

The excited state relaxation dynamics of V-shaped D-π-A systems having 4H-pyranylidene appended barbituric acid as an acceptor and diphenylamine (TPAPBA) and diethyl amine (EAPBA) as donors were investigated using steady-state and time-resolved spectroscopy along with theoretical optimization. The steady-state photophysical characterization exhibited the bathochromic shift of the emission maximum (∼6400 cm-1) and large change in the dipole moment (∼24D) with an increase of solvent polarity, reflecting the occurrence of the intramolecular charge transfer state (ICT) in the excited state. The nanosecond and femtosecond transient absorption spectra of these derivatives in a non-polar solvent, toluene, reveal that the excited state relaxation pathway involving a local excited state (LE) decayed to ICT followed by the formation of a twisted ICT state by conformational relaxation, finally leading to the triplet state. The lack of observation of a triplet state in the polar solvent, acetonitrile, signifies that the relaxation dynamics of V-shaped triads in the excited state are influenced by the polarity of the solvent.

Achieving efficient and stable blue thermally activated delayed fluorescence organic light-emitting diodes based on four-coordinate fluoroboron emitters by simple substitution molecular engineering.

Achieving both high efficiency and high stability in blue thermally activated delayed fluorescence organic light-emitting diodes (TADF-OLEDs) is challenging for practical displays and lighting. Here, we have successfully developed a series of sky-blue to pure-blue emitting donor-acceptor (D-A) type TADF materials featuring a four-coordinated boron with 2,2'-(pyridine-2,6-diyl)diphenolate (dppy) ligands, i.e.1-8. Synergistic engineering of substituents on the phenyl bridge as well as the electronic properties and the attached positions of heteroatom N-donors not only enables fine-tuning of the emission colors, but also modulates the nature and energies of their triplet excited states that are important for the reverse intersystem crossing (RISC). Particularly for the compound with two methyl substituents on the phenyl bridge (compound 8), RISC is significantly facilitated through the vibronic coupling of the energetically close-lying triplet charge transfer (3CT) and the triplet local excited (3LE) states, when compared to analogue 7. Efficient sky-blue to pure-blue OLEDs with electroluminescence peaks (λ EL) at 460-492 nm have been obtained, in which ca. five-fold higher external quantum efficiencies (EQEs) of 18.9% have been demonstrated by 8 than that by 7. Moreover, ca. thirty times longer device operational half-lifetimes (LT50) of 9113 hours for 8 than that for 7 as well as satisfactory LT50 reaching 26 643 hours for 6 at an initial luminance of 100 cd m-2 have also been demonstrated. To the best of our knowledge, these results represent one of the best high-performance blue OLEDs based on tetracoordinated boron TADF emitters. Moreover, the design strategy presented here has provided an attractive strategy for enhancing the device performance of blue TADF-OLEDs.

B-embedded disulfide-bridged π-conjugated compounds: structures and optical tuning.

Two novel B-embedded disulfide-bridged π-conjugated compounds (BS-CZ and BS-N) bearing different electron donor groups (phenyl carbazole and triphenylamine) have been prepared and show different optical mechanisms. The compound BS-CZ exhibits significant multiple resonance thermal activation delayed fluorescence (MR-TADF) properties with a small singlet-triplet energy gap (ΔEST = 0.16 eV) and a narrow half-peak full width (FWHM = 33 nm), while the compound BS-N shows traditional fluorescence luminescence (FL) characteristics with a larger ΔEST (0.28 eV) and FWHM (57 nm). Time-dependent density functional theory (TD-DFT) calculations show that the lowest excited singlet state (S1) of the compound BS-CZ exhibits local excited (LE) state characteristics, while the charge transfer (CT) state characteristics can be found in S1 of the compound BS-N. Considering good optical performance, the compound BS-CZ is used as an emitting layer of the organic light-emitting diode device and achieved saturated blue emission (473 nm) with a narrow FWHM (39 nm), and CIE color coordinates of (0.12, 0.21). This work provides an important strategy for the optical mechanism regulation and photoelectric applications of B-embedded disulfide-bridged π-conjugated molecules.

Windmill-type molecules for efficient deep-blue organic light-emitting diodes via hybridized local and charge-transfer excited state

High steric-hindrance windmill-type molecules exhibiting deep-blue light and large horizontal dipole ratio are designed. An efficient deep-blue device shows a maximum external quantum efficiency of 7.6% and a full width at half maximum of 55 nm.

Hybridized local and charge-transfer excited states of blue OLEDs based on phenanthroimidazole derivates with a narrow FWHM of 24 nm

Narrow FWHM achieved through fine tuning of excited state properties in HLCT materials.