Donor Acceptor Research Articles

Vinylene-Linked Covalent Organic Frameworks for Visible-Light-Promoted Selective Oxidation of Styrene in Water.

Vinylene-linked COFs, as an emerging class of crystalline porous polymers, have been regarded as ideal heterogenous photocatalysts due to their ordered structure, tailored pore size, outstanding stability and fully π-conjugated structure. Unfortunately, their photocatalytic performances are usually impeded by high exciton binding energy and unsatisfactory exciton dissociation efficiency. Herein, the authorsbroke through this dilemma by arrangement of complementary donor-acceptor (D-A) pairs within the COF skeleton to improve charge transfer/separation. Two vinylene-linked COFs (TMT-BT-COF and TMT-TT-COF) are synthesized by Aldol condensation using highly photoactive thienothiophene and benzothiazole groups as donor and electron-deficient triazine units as acceptor. Photochemical/electrochemical studies as well as DFT calculation suggest that these D-A type vinylene-linked COFs endow high charge transfer efficiency and low charge recombination. As a result, both of them demonstrate remarkably catalytic activity in the oxidation of styrene to benzaldehyde with molecular oxygen, with an exceptionally high conversion rate (≥92%) and selectivity (≥90%). Intriguingly, in the presence of NaHCO3, the above COFs could photocatalyze epoxidation styrene in water, and the styrene oxide selectivity reached 53%. This work elucidates the prominent capability of vinylene-linked COFs in the photocatalytic transformation of organic compounds in aqueous media, which may pave a new avenue for their future development.

Alkyl chain regulation of charge separation efficiency in edge-grafted g-C3N4 with carboxyl-alkyl substituted polythiophene for enhanced 2-mercaptobenzothiazole photodegradation

To investigate the effect of alkyl chain on the charge separation of photocatalyst, three mono-component edge-grafted g-C3N4 with carboxyl-substituted polythiophenes (CN-CSPs) were designed and synthesized, which chemically anchored polythiophenes to the edge of g-C3N4 framework by amide bond. Theoretical calculations reveal that the donor-acceptor (D-A) structure of the CN-CSPs positions the HOMO at the CSP donor and the LUMO at the heptazine ring acceptor, effectively enhancing intramolecular charge separation. Moreover, the alkyl chain connecting thiophene units to carboxyl groups significantly alters the electronegativity of the carboxyl groups, thereby influencing the dipole moment (DM). An increase in DM correlates with stronger intramolecular charge separation. The DM values of the CN-CSPs rank in the following order: CN-Me(5) (without alkyl) < CN-Et(3) (linear alkyl) < CN-Ma(3) (branched alkyl), consistent with the increasing order of their photocatalytic performance. This modification led to a 17-fold increase in the photocatalytic degradation of 2-mercaptobenzothiazole by the modified CN-Ma(3) compared to pure CN, demonstrating significant cyclic stability and overall enhanced performance of the photocatalytic system. The insights from this study offer valuable guidance for the chemical modification of g-C3N4 to boost photocatalytic efficiency.

SPLICER: a highly efficient base editing toolbox that enables in vivo therapeutic exon skipping

Exon skipping technologies enable exclusion of targeted exons from mature mRNA transcripts, which have broad applications in medicine and biotechnology. Existing techniques including antisense oligonucleotides, targetable nucleases, and base editors, while effective for specific applications, remain hindered by transient effects, genotoxicity, and inconsistent exon skipping. To overcome these limitations, here we develop SPLICER, a toolbox of next-generation base editors containing near-PAMless Cas9 nickase variants fused to adenosine or cytosine deaminases for the simultaneous editing of splice acceptor (SA) and splice donor (SD) sequences. Synchronized SA and SD editing improves exon skipping, reduces aberrant splicing, and enables skipping of exons refractory to single splice site editing. To demonstrate the therapeutic potential of SPLICER, we target APP exon 17, which encodes amino acids that are cleaved to form Aβ plaques in Alzheimer’s disease. SPLICER reduces the formation of Aβ42 peptides in vitro and enables efficient exon skipping in a mouse model of Alzheimer’s disease. Overall, SPLICER is a widely applicable and efficient exon skipping toolbox.

Understanding the Structural Modulations in Twisted Donor-Acceptor-Donor (D-A-D) Systems for Boosting Type I Photosensitizing Photocatalytic Activity.

Supramolecular assemblies based on the twisted donor-acceptor-donor (D-A-D) building block Qx-Ind have been developed, which interestingly, due to the balanced angle of twist (38.28°), high intermolecular charge transfer, and crystallization induced emission (CIE) characteristics, exhibit high molar absorptivity and a long-lived "lighted" excited state at the supramolecular level. The validity of the design concept was examined by preparing CIE active D-A-D system Qx-Indaz (weak donor, low angle of twist: 35.45°), in which, due to the insertion of an additional binding site for noncovalent interactions, a drastic change in the photophysical behavior is observed. The combined spectroscopic studies of all the compounds unveil the strong impact of modulation of the angle of twist and intermolecular charge transfer upon photophysical behavior in the aggregated state. Due to the favorable photophysical behavior, the supramolecular assemblies of Qx-Ind exhibit high type I photosensitizing activity in comparison to Qx-Indaz. The superior type I photosensitizing activity of Qx-Ind assemblies is manifested in their ability to efficiently catalyze the aerobic oxidative synthesis of quinazolin-4(3H)-ones (via type I ROS) from 2-aminobenzamide and aromatic aldehydes in the absence of additional additives (base/oxidant). Unlike photocatalytic nanoassemblies reported in the literature, due to the CIE characteristics, Qx-Ind does not require preliminary preparation and could be directly introduced in the solid state to reaction media. Thus, the present work demonstrates a simple strategy of upgrading type I photosensitizing activity by improving the ground/excited state behavior of a twisted D-A-D system through modulation of the angle of twist and charge transfer characteristics.

Atomic Zn-N4 Site-Regulated Donor-Acceptor Catalyst for Boosting Photocatalytic Bactericidal Activity.

Reactive oxygen species (ROS)-mediated photocatalytic antibacterial materials are emerging as promising alternatives for the antibiotic-free therapy of drug-resistant bacterial infections. However, the overall efficiency of photocatalytic sterilization is restricted by the rapid recombination of the charge carriers. Herein, we design an in-plane π-conjugated donor-acceptor (D-A) system (g-C3N4-Zn-NC), comprising graphitic carbon nitride (g-C3N4) as the donor and Zn single-atom anchored nitrogen-doped carbon (Zn-NC) as the acceptor. Experimental and theoretical results reveal that the introduction of Zn-NC induces the formation of an intermediate band in g-C3N4-Zn-NC, extending the spectral absorption range and facilitating charge carrier transfer and separation. Additionally, the synergistic effects of the dual sites, the N═C-N sites of the g-C3N4 "donor" and the atomic Zn-N4 sites of the Zn-NC "acceptor", boost ROS production. Consequently, the biocompatible g-C3N4-Zn-NC effectively kills methicillin-resistant Staphylococcus aureus (MRSA) under visible-light irradiation and promotes the healing of MRSA-infected wounds on mouse skin.

U-Shaped Dimeric Acceptors for Balancing Efficiency and Stability in Organic Solar Cells.

Despite significant improvements in power conversion efficiencies (PCEs) of organic solar cells (OSCs), achieving excellent stability remains a great challenge to their commercial feasibility. Here, U-shaped dimeric acceptors (5-IDT and 6-IDT) with different molecular lengths are introduced into the binary OSCs as a third component, respectively. The introduction of the third component effectively reduces the energetic disorder and non-radiative voltage losses and improves the exciton dissociation and charge transport of the devices. Consequently, the PCEs of the 6-IDT- and 5-IDT-treated OSCs are significantly improved to 19.32% and 19.96%, respectively, which is the highest PCE for oligomeric acceptors-based ternary OSCs to date. Meanwhile, the thermal stability of the treated devices is dramatically improved, with the initial efficiency retention of the 6-IDT- and 5-IDT-treated devices increasing from 18% to 32% and 75%, respectively, after 1000h of thermal stress. This is mainly attributed to the ability of the smaller molecular length of 5-IDT to stabilize the phase-separated morphology of the polymeric donor and small molecular acceptor, rather than the high glass transition temperature and low diffusion coefficient.

Machine learning assisted prediction of the nitric oxide (NO) solubility in various deep eutectic solvents

Deep eutectic solvents (DESs) are recently proposed as green materials to remove nitric oxide (NO) from released streams into the atmosphere. The mathematical aspect of this process attracted less attention than it deserved. A straightforward approach in this field will help engineer DES chemistry and optimize the equilibrium conditions to maximize the amount of removed NO. This study covers this gap by constructing a reliable artificial neural network (ANN) to correlate the NO removal capacity of DES with equilibrium pressure/temperature and solvent chemistry. So, firstly, the physical meaningful features are selected to make the DES chemistry quantitative. It was found that the density is the best representative for the hydrogen-bound acceptor and hydrogen-bound donor. Also, the density and viscosity of the DESs exhibit the highest correlation with the NO solubility. Then, the hyperparameters of three famous ANN types (feedforward, recurrent, and cascade) are determined by combining trial-and-error and sensitivity analyzes. Finally, the ranking test distinguishes the ANN type with the lowest uncertainty toward estimating NO dissolution in DESs. The cascade neural network (CNN) with twelve and one neurons in the hidden and output layers equipped with the tangent hyperbolic and radial basis transfer functions is identified as the best ANN type for the given purpose. This model predicts 292 DES-NO equilibrium records collected from the literature with mean absolute errors = 0.033, relative absolute errors = 1.49 %, mean squared errors = 0.002, and coefficient of determination = 0.9998. Also, the present study helps understand the role of DES chemistry and operating conditions on the amount of removable NO by DESs. 1,3-dimethylthioureaP4444Cl (3:1) is recognized as the best DES to separate NO molecules from gaseous streams, respectively. The simulation results show that the unit mass of the best DES is capable of absorbing up to ∼27 mol of NO.

Regulating Electron Acceptor Unit to Construct Conjugated Polymer Probe for Raman Imaging of Tumor and Sentinel Lymph Nodes.

Donor-acceptor (D-A) conjugated polymers have large Stokes shifts, high photostability, and good biocompatibility and thus are ideal for use as Raman probes in vivo. However, few D-A conjugated polymers are used as Raman probes for Raman imaging due to their weak Raman signal intensity and intrinsic fluorescence interference. Here, we developed a D-A conjugated polymer probe (CDT-TT) containing alternating cyclopentadithiophene-thienothiophene units for Raman imaging of tumor and sentinel lymph nodes (SLNs). The CDT-TT shows a strong Raman signal at 1389 cm-1 without fluorescence and lipid background signal interference under 785 nm near-infrared light. Moreover, the CDT-TT loaded nanoparticles realized the accurate imaging of tumor cells and tumor tissues. In addition, a high-resolution margin imaging of in situ SLNs was acquired. Taken together, the established method is effective for accurate Raman detection of tumors and SLNs, which may shed new light on the development of D-A polymer Raman probes for clinical imaging.

Improving Molecular Arrangement and Alleviating Nonradiative Energy Loss Using a Chlorinated Pyrido[3,4‐b]Quinoxaline‐Core‐Based Acceptor for High‐Performance Organic Solar Cells

AbstractThe electron‐deficient A1 unit in A‐DA1D‐A structured acceptors is critical for optimizing the efficiency of organic solar cells (OSCs). Drawing inspiration from the high performance of the previously reported pyrido[2,3‐b]quinoxaline‐core acceptors, Py6, an isomer of Py1 is designed with a repositioned pyridine nitrogen atom, and further modified it by chlorinating Py6 to create Py7. Theoretical calculations show that chlorine incorporation strengthens intermolecular non‐covalent interactions and promotes the tighter molecular stacking, as confirmed by grazing‐incidence wide‐angle X‐ray scattering. Consequently, D18/Py7 device delivers the enhanced fill factor and short‐circuit current density, compared to D18/Py1 and D18/Py6 device. Notably, D18/Py7 device also yields a higher open‐circuit voltage of 0.871 V, significantly outperforming Py1 (0.764 V) and Py6 (0.723 V), due to the low nonradiative energy losses. Further studies reveal that introducing Cl directs hole density toward the central pyrido[3,4‐b]quinoxaline unit and decreases the charge transfer state ratio of D18/acceptor. This prompts triplet‐to‐singlet conversion and reduces non‐radiative recombination losses. Additionally, using a mutual donor–acceptor dilution strategy, the (D18:1wt.% Py7)/(Py7:1wt.% D18) device achieves an impressive efficiency of 19.60%. This work emphasizes the great potential of the Py‐series acceptors and demonstrates that chlorine incorporation effectively reduces non‐radiative losses.

Effect of Alkyl Side Chain Length on Electrical Performance of Ion-Gel-Gated OFETs Based on Difluorobenzothiadiazole-Based D-A Copolymers

The performance of organic field-effect transistors (OFETs) is highly dependent on the dielectric–semiconductor interface, especially in ion-gel-gated OFETs, where a significantly high carrier density is induced at the interface at a low gate voltage. This study investigates how altering the alkyl side chain length of donor–acceptor (D-A) copolymers impacts the electrical performance of ion-gel-gated OFETs. Two difluorobenzothiadiazole-based D-A copolymers, PffBT4T-2OD and PffBT4T-2DT, are compared, where the latter features longer alkyl side chains. Although PffBT4T-2DT shows a 2.4-fold enhancement of charge mobility in the SiO2-gated OFETs compared to its counterpart due to higher crystallinity in the film, PffBT4T-2OD outperforms PffBT4T-2DT in the ion-gel-gated OFETs, manifested by an extraordinarily high mobility of 17.7 cm2/V s. The smoother surface morphology, as well as stronger interfacial interaction between the ion-gel dielectric and PffBT4T-2OD, enhances interfacial charge accumulation, which leads to higher mobility. Furthermore, PffBT4T-2OD is blended with a polymeric elastomer SEBS to achieve ion-gel-gated flexible OFETs. The blend devices exhibit high mobility of 8.6 cm2/V s and high stretchability, retaining 45% of initial mobility under 100% tensile strain. This study demonstrates the importance of optimizing the chain structure of polymer semiconductors and the semiconductor–dielectric interface to develop low-voltage and high-performance flexible OFETs for wearable electronics applications.

Dimeric BODIPY Donors Based on the Donor–Acceptor Structure for All-Small-Molecule Organic Solar Cells

Dimeric BODIPY Donors Based on the Donor–Acceptor Structure for All-Small-Molecule Organic Solar Cells

Harnessing the potential of coal-derived graphene oxide/epoxy nanocomposites: Enhancing thermal conductivity and fracture toughness

The choice of precursor material significantly influences the properties of graphene oxide (GO), thereby providing its adaptability across diverse applications. Coal, with its distinctive molecular structure characterized by graphene-like domains and aliphatic side chains, as well as abundant impurities and heteroatoms featuring specific functional groups, emerges as a promising precursor. Employing a recently developed facile one-pot process for synthesizing semianthracite coal-derived GO (AC-GO), we have, in this study, explored its potential as a nanofiller in an epoxy matrix, resulting in AC-GO-enriched nanocomposites. The main purpose of the project was to introduce AC-GO within the epoxy matrix to enhance its thermal conductivity and fracture resistance by enhancing interfacial interactions. Our findings indicate remarkable enhancements in thermal conductivity (0.646 Wm-1K-1 at 1.0 wt% loading) and fracture toughness (6.7 MPam1/2 at 0.8 wt% loading) within AC-GO loaded nanocomposites, with these improvements being 255 % and 215 %, respectively, over those for the epoxy matrix. Remarkably, they surpass those achieved with graphite-derived GO (Gr-GO) by approximately 112 % and 76 %, respectively. Enhancing thermal conductivity and fracture toughness in epoxy nanocomposites is vital for effective heat dissipation and durability, making them ideal for high-performance electronics, aerospace, and automotive applications. These improvements can be attributed to the enhanced interactions between oxygen moieties located at the periphery of AC-GO and the fundamental epoxy-amine hardener system within the resin formulation, fostering electron acceptor–donor interactions. Furthermore, we introduce a new figure of merit (FOM) that accurately captures the combined role of thermal conductivity and fracture toughness. It is shown that this FOM can serve as a useful design tool for selecting an optimal nanofiller loading for targeted applications. The findings of our paper highlight the versatility and unique attributes of AC-GO, offering promising opportunities for applications in the industrial engineering, owing to their outstanding interfacial properties.

Manipulating Intramolecular Charge Transfer in Terpyridine Derivatives Towards "Turn-On" Fluorescence Chemosensors for Zn2.

A series of donor-acceptor (D-A) terpyridine derivatives with various intramolecular charge transfer interactions have been successfully synthesized bearing phenyl, methoxyphenyl, N-butyldiphenylamine (DPA), and triphenylamine (TPA) as electron-donors and terpyridine (TPY), 2,6-di(pyrazin-2-yl)pyridine (PYDPZ), and N,N-dimethylated PYDPZ (PYDPZ-2CH3) as electron acceptors. Upon the introduction of pyrazine rings instead of pyridine ones and further selective N,N'-dimethylation, the intramolecular D-A interactions are significantly enhanced, resulting in the remarkable reduced intramolecular charge transfer (ICT) transitions and quenched PL emissions in CH2Cl2 solution. However, their ICT emissions are clearly recovered upon adding Zn2+. Especially, for double positively charged compound 12, the Zn2+-induced "turn-on" green emission (λmax, em=518 nm, Φ=0.24) with excellent sensitivity (I/I0=77) and selectivity (IZn/ICd=23) is detected. Under the optimized experimental condition (EtOH-H2O (9 : 1, v/v), containing 0.05 M HEPES buffer (pH=7.4)), this probe is used to quantitative determination of Zn2+ in a water sample with an average recovery of 97.5 %. Furthermore, the probe is applied to imaging of Zn2+ ions in HeLa cells and its mechanism is confirmed by the molecular dynamics simulation, in which lower coulomb potential for membrane surface adsorption and energy barrier for membrane translocation can be found.

Ferrocene Appended Linear Chromophores for Aggregation‐Induced Emission (AIE) and Nonlinear Optics (NLO): Combined Experimental and Theoretical Studies

AbstractNew nonlinear optical (NLO)‐active chromophores, featuring phenyl and methoxy phenyl substitutions at the D‐π‐A motif [(Fc‐C(C6H4‐R) = CH‐CH = C(CN)‐C6H4‐Br)] [R = H (1), OCH3 (2)] are synthesized and structurally analyzed. Chromophore 2 crystallized in a triclinic system (P‐1), consistent with DFT‐optimized structures. Non‐covalent interactions in the crystal packing suppress antiparallel alignment, enhancing SHG efficiencies. Molecular electrostatic potential (MEP) maps reveal structure‐property relationship and electronic communication between donor–acceptor moieties. Both chromophores exhibit suppressed emission in solution due to twisted intramolecular charge transfer (TICT) facilitated by the cyano vinylene group. However, Upon aggregation‐induced emission in a THF/H2O mixture, fluorescence significantly increases, attributed to restricted intramolecular rotation (RIR). Second Harmonic Generation (SHG) efficiencies, measured using the Kurtz–Perry powder technique with potassium dihydrogen phosphate (KDP) as a reference, show chromophore 2 is 1.1 times higher efficiency than chromophore 1. Density functional theory (DFT) derived hyperpolarizability values follow this trend, with chromophore 2 (β0 = 40.39 × 10−30 esu in B3LYP functional) surpassing chromophore 1. DFT and time‐dependent density functional theory (TD‐DFT) calculations employing B3LYP, CAM‐B3LYP, and LC‐BLYP functionals determined second‐order nonlinear optical parameters, B3LYP and CAM‐B3LYP produced values with minimal differences and a close correlation with the experimental results.

One pot synthesis of donor-acceptor carbon nitride with distinct thiophene rings accelerate photocatalytic hydrogen evolution

Graphitic carbon nitride (g-CN) with a donor-acceptor structure was synthesized by urea and cross-linking thiophene precursors at the terminal sites, achieved through calcination of urea with four different thiophene-based precursors under atmospheric conditions. Among these, UDB-2-1, which incorporates dibenzothiophene-2-carboxyaldehyde (DB-2) 1 mg, demonstrated a hydrogen evolution activity of 650 μmol/g·h, approximately six times higher than pristine graphitic carbon nitride (U). The apparent quantum yield (AQY) was measured to be 4.01 %, 4.89 %, and 3.72 % at 400 nm, 420 nm, and 450 nm, respectively, in the presence of potassium hydrogen phosphate (KPH). This enhanced performance is attributed to increased visible light absorption from the n-π∗ transition introduced by the thiophene ring and enhanced charge separation due to the donor-acceptor (DA) structure, with DB-2 acting as an electron donor. Prepared photocatalysts were characterized by XRD, XPS, FTIR, SEM, TEM, BET, ESR, EIS, Mott-Schottky, DRS, PL, and TRPL measurement. This study provides a simple and effective strategy to improve carbon nitride performance and underscores the importance of functional group positioning and structural isomers in molecular design for solar-energy applications.

Molecular engineering in thizolo[5,4-d]thiazole-based donor-acceptor covalent organic framework Induced high-efficient photosynthesis of H2O2

Covalent organic frameworks (COFs), as a newly emerging kind of porous and crystalline materials, serve as an ideal template for hydrogen peroxide (H2O2) photosynthesis. However, the vision of achieving high efficiency and selectivity in H2O2 photosynthesis is greatly hindered by the large exciton binding energy and limited charge separation efficiency influenced by the molecular structure of the building blocks. Herein, we developed three newly designed COFs with a donor–acceptor (D-A) structure and incorporated regulatory units (fluorine, F, and methoxyl, OCH3) in the D-A pathway through molecular engineering to optimize electronic structure, the availability of activate sites, charge kinetics and O2 activation capacity. Due to electron-donating effect, OCH3-functionalization (NIES-COF-3) can strengthen the intramolecular electron transfer and interaction with O2. This results in a reduction of the energy barrier of the rate-determining step (*O2 → *OOH) and excellent O2-to-H2O2 photocatalytic activity under visible light irradiation, delivering an H2O2 production rate of 3238.4 μmol g−1h−1 and a high apparent quantum yield of 3.17 %. In addition, F-functionalization (NIES-COF-2) primarily reduces the band-gap energy and improve the O2 adsorption capacity compared to unfunctionalized NIES-COF-1. This work unveils insight into the catalytic activity-optimization mechanism of molecular engineering in the D-A structure and provides important references for photocatalysts.

Charge Transfer Dynamics in Supramolecular Tessellations Composed of Aromatic Donors and Chiral Tris(naphthalenediimide) Triangular Acceptors.

Understanding charge transfer (CT) dynamics in donor-acceptor (D-A) cocrystals is important for the development of efficient organic photovoltaic and electronic materials. This study explores the photogenerated CT states of supramolecular tessellations formed by cocrystallizing a chiral tris(naphthalenediimide) triangular prism (-)-NDI-Δ with pyrene, perylene, and peri-xanthenoxanthene electron donors. By manipulating crystallization conditions, one-dimensional (1D) and two-dimensional (2D) cocrystals with distinct structural motifs and morphologies are achieved. Femtosecond and nanosecond transient absorption microscopies and time-resolved electron paramagnetic resonance spectroscopy were employed to elucidate the CT state dynamics. Our findings reveal that the CT state lifetimes are lengthened in the 2D cocrystals relative to the 1D cocrystals, which is attributable to the symmetry and molecular packing differences between them that modulate the CT interactions. This work highlights the potential of using preorganized covalent multisite charge carriers as donors or acceptors in cocrystals as a strategy for engineering structures for advanced multifunctional materials with tunable CT properties.

Donor-Acceptor Viologens with Through-Space Conjugation for Enhanced Visible-Light-Driven Photocatalysis.

A series of novel donor-acceptor (D-A) type viologens with through-space conjugation (TSC) are synthesized. The synergistic effect of D-A conjugation and TSC endow these compounds with a narrower energy gap, excellent redox properties, strong absorption in the visible range (up to 450nm), and high efficiency of intramolecular charge transfer (ICT). These compounds also exhibit a long-lived charge separation state and stable radical formation. Considering their impressive photophysical and redox properties, TSC viologens with D-A conjugation are explored for visible-light-driven photocatalysis. As a catalyst in oxidative coupling reactions under visible light, compound 9 can achieve a yield of 94%, attributed to its strong ICT effect. Additionally, hybridized into graphitic carbon nitride (g-C₃N₄), compound 9 enhances hydrogen production performance under visible light, achieving an H2 generation rate of 4102µmolh-1g-1. This study highlights the potential applications of TSC viologens in photocatalytic systems.

Boosting Photoconductivity by Increasing the Structural Complexity of Multivariate Covalent Organic Frameworks.

The assessment of the photoconductivity of Donor-Acceptor (D-A) ordered bulk heterojunctions is gaining attention for the development of innovative organic semiconductors in optoelectronics. Here, the synthesis of pyrene-based (D) Covalent Organic Frameworks, achieve through a multivariate reaction involving two distinct acceptors is reported (A). The products are characterized using powder x-ray diffraction, N2 sorption isotherms, electronic microscopy, and in silico calculations, among other techniques. These characterizations reveal that the multicomponent synthesis enables the modification of properties (e.g., bandgap) of the framework while preserving its structural features, such as crystallinity and porosity. The ordered D-A arrays position these materials as promising candidates for photoconductive semiconductors, particularly regarding the variation in the composition of isotopological frameworks. Photoconductivity experiments demonstrate a volcano-type correlation with respect to the A moiety content, with the optimal value reaching 7.9 × 10-5 cm2 V-1 s-1 for the bare NIP25%-COF. This study illustrates how introducing diverse acceptor units through multivariate synthesis can enhance the photoconductivity of these materials via "defect" engineering, without sacrificing their crystalline or porous characteristics and avoiding the need for de novo synthesis.

Enhancing Internal Electric Field of Metal-Free Donor-Acceptor Conjugated Photocatalysts for Efficient Photocatalytic Degradation of Tetracycline and CO2 Reduction.

Constructing alternating donor-acceptor (D-A) units within g-C3N4 represents an effective strategy for enhancing photocatalytic performance through improved charge carrier separation while concurrently addressing energy shortages and facilitating wastewater remediation. Here, a series of D-A-type conjugated photocatalysts (CNBTC-X) are prepared using g-C3N4 as an acceptor unit and different masses of 5-bromo-2-thiophenecarboxaldehyde (BTC) as a donor unit by a one-step thermal polymerization. CNBTC-50 presents higher photocatalytic properties for CO2 reduction coupled with tetracycline (TC) removal than those of g-C3N4, CNBTC-10, CNBTC-30, and CNBTC-70. The introduction of the unique electron-donor-acceptor structure effectively drives the separation and transfer of photoinduced carriers while reducing the internal carrier transfer hindrance. Photocatalytic experiments reveal that the CNBTC-50 photocatalyst achieves up to 94.6% TC removal under visible light irradiation conditions. Compared with that of the pristine g-C3N4, the photocatalytic degradation reaction rate constant of CNBTC-50 is significantly increased by about 3.87 times. The study examines the influence of various reaction parameters on degradation activity, including catalyst concentration, pH, and TC concentration. Additionally, LC-MS is utilized to perform a comprehensive analysis of the intermediates and pathways involved in TC degradation. Furthermore, CNBTC-50 demonstrates remarkable photocatalytic CO2 reduction activity, achieving rates of 20.83 μmol g-1 h-1 (CO) and 9.36 μmol g-1 h-1 (CH4), which are 10.68 and 5.98 times more efficient than those of g-C3N4, respectively. This work aims to offer valuable guidance for the rational design of nonmetal D-A-structured catalysts and effectively integrates reaction systems to couple CO2 reduction with antibiotic removal.