Intermolecular Electron Transfer Research Articles

Viologen‐based host–guest supramolecule with tunable intramolecular/intermolecular electron transfer chromism and dynamic fluorescence

AbstractViologen, as a type of strong electron acceptor, is prone to undergo electron transfer (ET) and change color under external stimuli. However, due to the easy aggregation of viologen molecules, they usually suffer from poor fluorescence emission in the condensed phase. Herein, a new viologen derivative of VioCl2·2Cl (12+·2Cl) was designed and synthesized, in which the fluorescence was enhanced by introducing Me‐β‐CD to weaken the interactions between viologen molecules. Then a viologen‐based host–guest supramolecule of 12+@Me‐β‐CD was obtained by electrostatic interactions. Photo‐/chemo‐responded guest 12+ supplies 12+@Me‐β‐CD, a green and dark purple caused by intramolecular and intermolecular ET. Furthermore, 12+@Me‐β‐CD displays an additional thermal responsive purple color. The triple chromic behaviors all exhibit excellent reversibility and cycling stability. As expected, 12+@Me‐β‐CD exhibits strong photoluminescence (PL) in solid–liquid dual states, presenting an improved quantum yield (Φ) from 12+ (Φs = 0.37%, Φl = 16.74%) to 12+@Me‐β‐CD (Φs = 10.45%, Φl = 25.86%), and the fluorescence intensity can be dynamically modulated by light, heat, and acid/base vapors. The multi‐responsive chromism and tunable fluorescence of 12+@Me‐β‐CD allow for potential applications in information security and smart windows.

Intermolecular Proton-Coupled Electron Transfer Reactivity from a Persistent Charge-Transfer State for Reductive Photoelectrocatalysis.

Interest in applying proton-coupled electron transfer (PCET) reagents in reductive electro- and photocatalysis requires strategies that mitigate the competing hydrogen evolution reaction. Photoexcitation of a PCET donor to a charge-separated state (CSS) can produce a powerful H-atom donor capable of being electrochemically recycled at a comparatively anodic potential corresponding to its ground state. However, the challenge is designing a mediator with a sufficiently long-lived excited state for bimolecular reactivity. Here, we describe a powerful ferrocene-derived photoelectrochemical PCET mediator exhibiting an unusually long-lived CSS (τ ∼ 0.9 μs). In addition to detailed photophysical studies, proof-of-concept stoichiometric and catalytic proton-coupled reductive transformations are presented, which illustrate the promise of this approach.

Design of Dyes Based on the Quinoline or Quinoxaline Skeleton towards Visible Light Photoinitiators.

Dyes based on quinoline and quinoxaline skeletons were designed for application as visible light photoinitiators. The obtained compounds absorb electromagnetic radiation on the border between ultraviolet and visible light, which allows the use of dental lamps as light sources during the initiation of the photopolymerization reaction. Their another desirable feature is the ability to create a long-lived excited state, which enables the chain reaction to proceed through the mechanism of intermolecular electron transfer. In two-component photoinitiating systems, in the presence of an electron donor or a hydrogen atom donor, the synthesized compounds show excellent abilities to photoinitiate the polymerization of acrylates. In control tests, the efficiency of photopolymerization using modified quinoline and quinoxaline derivatives is comparable to that obtained using a typical, commercial photoinitiator for dentistry, camphorquinone. Moreover, the use of the tested compounds requires a small amount of photoinitiator (only 0.04% by weight) to initiate the reaction. The research also showed a significant acceleration of the photopolymerization process and shortening of the reaction time. In practice, this means that the new two-component initiating systems can be used in much lower concentrations without slowing down the speed of obtaining polymer materials. It is worth emphasizing that these two features of the new initiating system allow for cost reduction by reducing financial outlays on both materials (photoinitiators) and electricity.

Photoactivated Circularly Polarized Luminescent Organic Radicals in Doped Amorphous Polymer

AbstractLuminescent organic radicals, especially those with photoactivated circularly polarized luminescence (CPL) features, hold great significance for cutting‐edge optoelectronic applications, but their development still remains a challenge. In this study, we propose a novel strategy to achieve photoactivated CPL radicals by bonding two phosphine centers within an axial chiral system, yielding a compound of R/S‐5,5‐bis(diphenylphosphino)‐4,4′‐bibenzo[d][1,3]dioxole (R/S‐BDP). The photoactivated R/S‐BDP molecules in polymer matrix display a robust quantum yield of 19.8 % and a dissymmetry factor (glum) of 1.2×10−4, marking this work as the first example of photoactivated CPL radicals. Furthermore, the glum is improved to 1.0×10−2 by using a liquid crystal as host. Experimental and theoretical analyses reveal that R/S‐BDP molecules, endowed with double phosphine cores in axial chirality, offer a direct way for intramolecular electron transfer upon photoirradiation. This leads to the generation of radical ionic pairs, which subsequently trigger the donor‐acceptor arrangement through intermolecular electron transfer, thereby resulting in stable radical emission. The extended photoactivated BDP‐F exhibits a remarkably high quantum efficiency of 57.8%. Ultimately, the distinctive photo‐responsive CPL radical luminescence has been successfully used for information displays and anti‐counterfeiting.

Photoactivated Circularly Polarized Luminescent Organic Radicals in Doped Amorphous Polymer.

Luminescent organic radicals, especially those with photoactivated circularly polarized luminescence (CPL) features, hold great significance for cutting-edge optoelectronic applications, but their development still remains a challenge. In this study, we propose a novel strategy to achieve photoactivated CPL radicals by bonding two phosphine centers within an axial chiral system, yielding a compound of R/S-5,5-bis(diphenylphosphino)-4,4'-bibenzo[d][1,3]dioxole (R/S-BDP). The photoactivated R/S-BDP molecules in polymer matrix display a robust quantum yield of 19.8 % and a dissymmetry factor (glum) of 1.2×10-4, marking this work as the first example of photoactivated CPL radicals. Furthermore, the glum is improved to 1.0×10-2 by using a liquid crystal as host. Experimental and theoretical analyses reveal that R/S-BDP molecules, endowed with double phosphine cores in axial chirality, offer a direct way for intramolecular electron transfer upon photoirradiation. This leads to the generation of radical ionic pairs, which subsequently trigger the donor-acceptor arrangement through intermolecular electron transfer, thereby resulting in stable radical emission. The extended photoactivated BDP-F exhibits a remarkably high quantum efficiency of 57.8%. Ultimately, the distinctive photo-responsive CPL radical luminescence has been successfully used for information displays and anti-counterfeiting.

Earth-abundant Zn-dipyrrin chromophores for efficient CO2 photoreduction

Abstract Developing strong sensitizing and earth-abundant antenna molecules are highly desirable for CO2 reduction through artificial photosynthesis. Herein, a library of Zn-dipyrrin complexes (Z-1−Z-6) were rationally designed via precisely controlling their molecular configuration to optimize strong sensitizing earth-abundant photosensitizers. Upon visible light excitation, their special geometry enables intramolecular charge transfer to induce charge transfer state, which was firstly demonstrated to accept electrons from electron donor. The resulting long-lived reduced photosensitizer was confirmed to trigger consecutive intermolecular electron transfers for boosting CO2-to-CO conversion. Remarkably, the earth-abundant catalytic system with Z-6 and Fe-catalyst exhibits outstanding performance with over 20 000 turnover number and 29.7% quantum yield, representing an excellent catalytic performance among the molecular catalytic systems, and much superior to that of noble-metal photosensitizer Ir(ppy)2(bpy)+ under the similar condition. Experimental and theoretical investigations comprehensively unveil the structure-activity relationship, opening up a new horizon to develop earth-abundant strong sensitizing chromophores for boosting artificial photosynthesis.

Highly efficient one-component benzylidene cyclopentanone initiators for visible light polymerization

Visible light polymerization is a development trend in the field of photocuring. However, most of the reported visible light photoinitiators (PIs) are two-component systems that display limited initiation efficiency due to diffusion restriction and back electron transfer effect. In this study, two one-component visible light PIs (BDNPG-1 and BDNPG-2) are synthesized through combining N-phenylglycine (NPG) moiety with cyclopentanone moiety together. Upon irradiation of blue or green light, they can undergo intermolecular electron transfer followed by proton transfer plus a decarboxylation reaction to produce carbon dioxide and aminoalkyl radicals. This decarboxylation reaction is irreversible so that the intermolecular back electron transfer can be effectively blocked, resulting in a significantly improved photoinitiation efficiency of BDNPG-1 and BDNPG-2 compared with their prototype PI (BDEA) containing no NPG group and the two-component system of BDEA+NPG. Furthermore, both of them have strong two-photon absorption capability and show excellent performance in two-photon polymerization.

Organic nanoparticles based on aza-boron dipyrromethene derivatives for combined photothermal and photodynamic cancer therapy

Cancer is one of the major diseases that threaten human being's health and life. Recently, phototherapy has gained great attention due to the advantages of high selectivity and low toxicity. Nonetheless, the development a single photosensitizer capable of simultaneously achieving photothermal and photodynamic effects remains a great challenge. Aza-boron-dipyrromethene (aza-BODIPY) dyes have been widely studied in biomedical area for their significant absorption in the near infrared region and high fluorescence quantum yield. In this contribution, three aza-BODIPY molecules (TAS-BP, TES-BP and TESO-BP) that conjugated with triphenylamine (TPA) or tetraphenylethylene (TPE) were designed and synthesized. The presence of donor-acceptor-donor pairs within compounds enables the intermolecular electron transfer, leading to the augmentation of near-infrared (NIR) absorbance and the generation of non-radiative heat. The nanoparticles were prepared via the assembly of the related organic compounds with amphiphilic polymer (DSPE-PEG2000), which were named as TAS-BP NPs, TES-BP NPs and TESO-BP NPs, respectively. Importantly, three nanoparticles can generate heat and reactive oxygen species (ROS) simultaneously induced by a single laser (808 nm). The photothermal conversion efficiency of TAS-BP NPs, TES-BP NPs and TESO-BP NPs were determined to be 64.5%, 65.7%, and 53.6%, respectively. Furthermore, the cellular experiments demonstrated the good biocompatibility and outstanding photocytotoxicity of three nanoparticles, and the TES-BP NPs exhibited the highest photodynamic/photothermal synergistic effect. Thus, the as-prepared organic nanomaterials were demonstrated as potential candidates for cancer treatment through phototherapy.

Characterization of ferredoxins involved in electron transfer pathways for nitrogen fixation implicates differences in electronic structure in tuning 2[4Fe[sbnd]4S] Fd activity

Ferredoxins (Fds) are small proteins which shuttle electrons to pathways like biological nitrogen fixation. Physical properties tune the reactivity of Fds with different pathways, but knowledge on how these properties can be manipulated to engineer new electron transfer pathways is lacking. Recently, we showed that an evolved strain of Rhodopseudomonas palustris uses a new electron transfer pathway for nitrogen fixation. This pathway involves a variant of the primary Fd of nitrogen fixation in R. palustris, Fer1, in which threonine at position 11 is substituted for isoleucine (Fer1T11I). To understand why this substitution in Fer1 enables more efficient electron transfer, we used in vivo and in vitro methods to characterize Fer1 and Fer1T11I. Electrochemical characterization revealed both Fer1 and Fer1T11I have similar redox transitions (−480 mV and − 550 mV), indicating the reduction potential was unaffected despite the proximity of T11 to an iron‑sulfur (FeS) cluster of Fer1. Additionally, disruption of hydrogen bonding around an FeS cluster in Fer1 by substituting threonine with alanine (T11A) or valine (T11V) did not increase nitrogenase activity, indicating that disruption of hydrogen bonding does not explain the difference in activity observed for Fer1T11I. Electron paramagnetic resonance spectroscopy studies revealed key differences in the electronic structure of Fer1 and Fer1T11I, which indicate changes to the high spin states and/or spin-spin coupling between the FeS clusters of Fer1. Our data implicates these electronic structure differences in facilitating electron flow and sets a foundation for further investigations to understand the connection between these properties and intermolecular electron transfer.

Multimetal-Based Metal-Organic Framework System for the Sensitive Detection of Heart-Type Fatty Acid Binding Protein in Electrochemiluminescence Immunoassay.

In this work, an electrochemiluminescence (ECL) quenching system using multimetal-organic frameworks (MMOFs) was proposed for the sensitive and specific detection of heart-type fatty acid-binding protein (H-FABP), a marker of acute myocardial infarction (AMI). Bimetallic MOFs containing Ru and Mn as metal centers were synthesized via a one-step hydrothermal method, yielding RuMn MOFs as the ECL emitter. The RuMn MOFs not only possessed the strong ECL performance of Ru(bpy)32+ but also maintained high porosity and original metal active sites characteristic of MOFs. Moreover, under the synergistic effect of MOFs and Ru(bpy)32+, RuMn MOFs have more efficient and stable ECL emission. The trimetal-based MOF (FePtRh MOF) was used as the ECL quencher because of the electron transfer between FePtRh MOFs and RuMn MOFs. In addition, active intramolecular electron transfer from Pt to Fe or Rh atoms also occurred in FePtRh MOFs, which could promote intermolecular electron transfer and improve electron transfer efficiency to enhance the quenching efficiency. The proposed ECL immunosensor demonstrated a wide dynamic range and a low detection limit of 0.01-100 ng mL-1 and 6.8 pg mL-1, respectively, under optimal conditions. The ECL quenching system also presented good specificity, stability, and reproducibility. Therefore, an alternative method for H-FABP detection in clinical diagnosis was provided by this study, highlighting the potential of MMOFs in advancing ECL technology.

Deciphering Oxygen‐Independent Augmented Photodynamic Oncotherapy by Facilitating the Separation of Electron‐Hole Pairs

AbstractDeveloping Type‐I photosensitizers provides an attractive approach to solve the dilemma of inadequate efficacy of photodynamic therapy (PDT) caused by the inherent oxygen consumption of traditional Type‐II PDT and anoxic tumor microenvironment. The challenge for the exploration of Type‐I PSs is to facilitate the electron transfer ability of photosensitization molecules for transforming oxygen or H2O to reactive oxygen species (ROS). Herein, we propose an electronic acceptor‐triggered photoinduced electron transfer (a‐PET) strategy promoting the separation of electron‐hole pairs by marriage of two organic semiconducting molecules of a non‐fullerene scaffold‐based photosensitizer and a perylene diimide that significantly boost the Type‐I PDT pathway to produce plentiful ROS, especially, inducing 3.5‐fold and 2.5‐fold amplification of hydroxyl (OH⋅) and superoxide (O2−⋅) generation. Systematic mechanism exploration reveals that intermolecular electron transfer and intramolecular charge separation after photoirradiation generate a competent production of radical ion pairs that promote the Type‐I PDT process by theoretical calculation and ultrafast femtosecond transient absorption (fs‐TA) spectroscopy. By complementary tumor diagnosis with photoacoustic imaging and second near‐infrared fluorescence imaging, this as‐prepared nanoplatform exhibits fabulous photocytotoxicity in harsh hypoxic conditions and terrific cancer revoked abilities in living mice. We envision that this work will broaden the insight into high‐efficiency Type‐I PDT for cancer phototheranostics.

Deciphering Oxygen-Independent Augmented Photodynamic Oncotherapy by Facilitating the Separation of Electron-Hole Pairs.

Developing Type-I photosensitizers provides an attractive approach to solve the dilemma of inadequate efficacy of photodynamic therapy (PDT) caused by the inherent oxygen consumption of traditional Type-II PDT and anoxic tumor microenvironment. The challenge for the exploration of Type-I PSs is to facilitate the electron transfer ability of photosensitization molecules for transforming oxygen or H2O to reactive oxygen species (ROS). Herein, we propose an electronic acceptor-triggered photoinduced electron transfer (a-PET) strategy promoting the separation of electron-hole pairs by marriage of two organic semiconducting molecules of a non-fullerene scaffold-based photosensitizer and a perylene diimide that significantly boost the Type-I PDT pathway to produce plentiful ROS, especially, inducing 3.5-fold and 2.5-fold amplification of hydroxyl (OH⋅) and superoxide (O2 -⋅) generation. Systematic mechanism exploration reveals that intermolecular electron transfer and intramolecular charge separation after photoirradiation generate a competent production of radical ion pairs that promote the Type-I PDT process by theoretical calculation and ultrafast femtosecond transient absorption (fs-TA) spectroscopy. By complementary tumor diagnosis with photoacoustic imaging and second near-infrared fluorescence imaging, this as-prepared nanoplatform exhibits fabulous photocytotoxicity in harsh hypoxic conditions and terrific cancer revoked abilities in living mice. We envision that this work will broaden the insight into high-efficiency Type-I PDT for cancer phototheranostics.

Intermolecular photoinduced electron transfer in biosystems: impact of conformational transitions and multiple channels on kinetics

Estimating the kinetics of electron transfer (ET) processes in biologically relevant systems using theoretical‐computational methods remains a formidable task. This challenge arises from the inherent complexity of these systems, which makes it impractical to apply a fully quantum‐mechanical treatment. Hybrid quantum mechanical/classical mechanical computational approaches have been devised to enable the explicit simulation of electron transfer kinetics. This concept article focuses on a specific theoretical‐computational method employed in this context, namely the Perturbed Matrix Method (PMM), which has the merit of being able to include large‐scale conformational effects in the ET kinetics and potential multiple, alternative, ET channels. We describe its underlying physical principles, examine its advantages and limitations, and offer insights into its applications. Examples of the approach are discussed in the context of estimating photo‐induced electron transfer kinetics in proteins. The non‐exponential behavior observed in the presented case studies arises mainly from an active coupling with the environment fluctuations, but partly also stems from the presence of branching ET pathways.

Photo‐Induced Disproportionation‐Mediated Photodynamic Therapy: Simultaneous Oxidation of Tetrahydrobiopterin and Generation of Superoxide Radicals

AbstractWe herein present an approach of photo‐induced disproportionation for preparation of Type‐I photodynamic agents. As a proof of concept, BODIPY‐based photosensitizers were rationally designed and prepared. The photo‐induced intermolecular electron transfer between homotypic chromophores leads to the disproportionation reaction, resulting in the formation of charged intermediates, cationic and anionic radicals. The cationic radicals efficiently oxidize the cellularimportant coenzyme, tetrahydrobiopterin (BH4), and the anionic radicals transfer electrons to oxygen to produce superoxide radicals (O2−⋅). One of our Type‐I photodynamic agents not only self‐assembles in water but also effectively targets the endoplasmic reticulum. It displayed excellent photocytotoxicity even in highly hypoxic environments (2 % O2), with a half‐maximal inhibitory concentration (IC50) of 0.96 μM, and demonstrated outstanding antitumor efficacy in murine models bearing HeLa tumors.

Photo-Induced Disproportionation-Mediated Photodynamic Therapy: Simultaneous Oxidation of Tetrahydrobiopterin and Generation of Superoxide Radicals.

We herein present an approach of photo-induced disproportionation for preparation of Type-I photodynamic agents. As a proof of concept, BODIPY-based photosensitizers were rationally designed and prepared. The photo-induced intermolecular electron transfer between homotypic chromophores leads to the disproportionation reaction, resulting in the formation of charged intermediates, cationic and anionic radicals. The cationic radicals efficiently oxidize the cellularimportant coenzyme, tetrahydrobiopterin (BH4 ), and the anionic radicals transfer electrons to oxygen to produce superoxide radicals (O2 - ⋅). One of our Type-I photodynamic agents not only self-assembles in water but also effectively targets the endoplasmic reticulum. It displayed excellent photocytotoxicity even in highly hypoxic environments (2 % O2 ), with a half-maximal inhibitory concentration (IC50 ) of 0.96 μM, and demonstrated outstanding antitumor efficacy in murine models bearing HeLa tumors.

Destabilization of spin-Peierls phase via a charge-spin modulated Floquet state induced by intramolecular vibrational excitation

The electronic state control using a periodic light field is one of the central subjects in photophysics. In molecular solids, intramolecular vibrations sometimes couple to intermolecular electron transfer, thus modulating electron and spin densities of each molecule. Here, we show that in a quasi-one-dimensional molecular solid K-tetracyanoquinodimethane (TCNQ) in which TCNQ molecules are dimerized by the spin-Peierls mechanism, an intramolecular vibrational excitation with a phase-locked mid-infrared pulse induces a charge-spin modulated Floquet state, which destabilizes the spin-Peierls phase. By detecting reflectivity changes of the intramolecular transition band along the mid-infrared electric field with 6.6-fs probe pulses, we detected high-frequency oscillations reflecting electron- and spin-density modulations synchronized with intramolecular vibrations. More significantly, we observed an oscillation of ~110 cm−1 due to a dimeric mode driven by a decrease in spin-Peierls dimerization. This dimerization reduction was confirmed by measuring transient reflectivity changes of the Mott-gap transition band. These results demonstrate the effectiveness of intramolecular vibrational excitation as a method for Floquet engineering in molecular solids.

Bielectrode Strategy for Determination of CYP2E1 Catalytic Activity: Electrodes with Bactosomes and Voltammetric Determination of 6-Hydroxychlorzoxazone.

We describe a bielectrode system for evaluation of the electrocatalytic activity of cytochrome P450 2E1 (CYP2E1) towards chlorzoxazone. One electrode of the system was employed to immobilize Bactosomes with human CYP2E1, cytochrome P450 reductase (CPR), and cytochrome b5 (cyt b5). The second electrode was used to quantify CYP2E1-produced 6-hydroxychlorzoxazone by its direct electrochemical oxidation, registered using square-wave voltammetry. Using this system, we determined the steady-state kinetic parameters of chlorzoxazone hydroxylation by CYP2E1 of Bactosomes immobilized on the electrode: the maximal reaction rate (Vmax) was 1.64 ± 0.08 min-1, and the Michaelis constant (KM) was 78 ± 9 μM. We studied the electrochemical characteristics of immobilized Bactosomes and have revealed that electron transfer from the electrode occurs both to the flavin prosthetic groups of CPR and the heme iron ions of CYP2E1 and cyt b5. Additionally, it has been demonstrated that CPR has the capacity to activate CYP2E1 electrocatalytic activity towards chlorzoxazone, likely through intermolecular electron transfer from the electrochemically reduced form of CPR to the CYP2E1 heme iron ion.

PH/GSH dual responsive nanosystem for nitric oxide generation enhanced type I photodynamic therapy

Tumor hypoxia diminishes the effectiveness of traditional type II photodynamic therapy (PDT) due to oxygen consumption. Type I PDT, which can operate independently of oxygen, is a viable option for treating hypoxic tumors. In this study, we have designed and synthesized JSK@PEG-IR820 NPs that are responsive to the tumor microenvironment (TME) to enhance type I PDT through glutathione (GSH) depletion. Our approach aims to expand the sources of therapeutic benefits by promoting the generation of superoxide radicals (O2−.) while minimizing their consumption. The diisopropyl group within PEG-IR820 serves a dual purpose: it functions as a pH sensor for the disassembly of the NPs to release JSK and enhances intermolecular electron transfer to IR820, facilitating efficient O2−. generation. Simultaneously, the release of JSK leads to GSH depletion, resulting in the generation of nitric oxide (NO). This, in turn, contributes to the formation of highly cytotoxic peroxynitrite (ONOO−.), thereby enhancing the therapeutic efficacy of these NPs. NIR-II fluorescence imaging guided therapy has achieved successful tumor eradication with the assistance of laser therapy.

Controlled intermolecular proton-coupled electron transfer process: a novel design strategy for highly sensitive piezo-chromic fluorescent materials

Highly sensitive piezochromic fluorescent materials were successfully synthesized via a controlled intermolecular proton-coupled electron transfer process in single-benzene π-system.

Pressure effects on both fluorescent emission and charge transport properties of organic semiconductors: a computational study.

External pressure can regulate the photophysical property and charge transport performance of organic semiconductors, however, the underlying mechanism at the microscopic level is still elusive. Using thermal vibrational correlation function coupled quantum mechanics/molecular mechanics and full quantum charge transfer rate theory, we systematically explore the influence of pressure on fluorescence emission and charge transport behaviours of representative cyclooctatetrathiophene (COTh). It is found that, upon pressurization, the intramolecular configurations of COTh became more twisted, leading to the blue-shifted emission. The fluorescence quantum efficiency (FQE) of COTh crystals decreases monotonically in a wide pressure range of 0-4.38 GPa, because the increase of intermolecular electronic energy transfer rate constant (keet) is larger than the decrease of internal conversion rate constant (kic), and the variation of keet is dominant. The decrease in kic is attributed to the decreasing reorganization energy, reflecting the suppression of the low-frequency flipping vibrations of four thiophene rings and the high-frequency stretching vibrations of central cyclooctatetraene, while the keet increase is due to the simultaneous increase in exciton coupling and spectra overlap. Moreover, we predicted that the hole mobility of COTh increases monotonically by nearly an order of magnitude from 0.39 to 3.00 cm2 V-1 s-1 upon compression, because of the increase in transfer integral and the decrease of charged reorganization energy. Furthermore, its hole mobility exhibits obvious anisotropy. Our work systematically builds the external pressure, molecular packing, luminescence and transport properties relationships of organic semiconductors and provides theoretical guidance for the rational design of pressure responsive organic semiconductors with excellent photoelectric performance.