Ultrafast and Coherent Dynamics in a Solvent Switchable "Pink Box" Perylene Diimide Dimer.

Perylene diimide (PDI) dimers and higher aggregates are key components in organic molecular photonics and photovoltaic devices, supporting singlet fission and symmetry breaking charge separation. Detailed understanding of their excited states is thus important. This has proven challenging because interchromophoric coupling is a strong function of dimer architecture. Recently, a macrocyclic PDI dimer was reported in which excitonic coupling could be turned on and off simply by changing the solvent. This presents a useful case where coupling is modified without synthetic changes to tune supramolecular structure. Here we present a detailed study of solvent dependent excited state dynamics in this dimer by means of coherent multidimensional spectroscopy. Spectral analysis resolves the different coupling strengths, which are consistent with solvent dependent changes in dimer conformation. The strongly coupled conformer forms an excimer within 300 fs. The low-frequency Raman active modes recovered from two-dimensional electronic spectra reveal frequencies characteristic of exciton coupling. These are assigned to modes modulating the coupling from the corresponding DFT calculations. Further analysis reveals a time dependent frequency during excimer formation. Analysis of two-dimensional "beatmaps" reveals features in the coupled dimer which are not predicted by the displaced harmonic oscillator model and are assigned to vibronic coupling.

Non-ionic Perylene-Diimide Polymer as Universal Cathode Interlayer for Conventional, Inverted, and Blade-Coated Organic Solar Cells.

As a class of predominantly used cathode interlayers (CILs) in organic solar cells (OSCs), perylene-diimide (PDI)-based polymers exhibit intriguing characteristics of excellent charge transporting capacity and suitable energy levels. Despite that, PDI-based CILs with satisfied film-forming ability and adequate solvent resistance are rather rare, which not only limits the further advance of OSC performances but also hinders the practical use of PDI CILs. Herein, we designed and synthesized two non-conjugated PDI polymers for achieving high power conversion efficiency (PCE) in diverse types of OSCs. The utilization of oligo (ethylene glycol) (OEG) linkage enhanced the n-doping effect of PDI polymers, leading to an improved ability of the CIL to reduce work function and improve electron transporting capability. Moreover, the introduction of the non-ionic OEG chain effectively improve the wetting property and solvent resistance of PDI polymers, so the PPDINN CIL can withstand diverse processing conditions in fabricating different OSCs, including conventional, inverted and blade-coated devices. The binary OSC with conventional structure using PPDINN CIL showed a PCE of 18.6%, along with an improved device stability. Besides, PPDINN is compatible with the large-area blade-coating technique, and a PCE of 16.6% was achieved in the 1-cm2 OSC where a blade-coated PPDINN was used.

Integration of Perylene Diimide into a Covalent Organic Framework for Photocatalytic Oxidation.

Perylene diimides (PDIs) have garnered considerable attention due to its immense potential in photocatalysis. However, manipulating the molecular packing within their aggregates and enhancing the efficiency of photogenerated carrier recombination remain significant challenges. In this study, we demonstrate the incorporation of a PDI unit into a covalent organic framework (COF), named PDI-PDA, by linking an ortho-substituted PDI with p-phenylenediamine (PDA) to control its intermolecular aggregation. The incorporation enables precise modulation of electron transfer dynamics, leading to a ten-fold increase in the efficiency of photocatalytic oxidation of thioether to sulfoxide with PDI-PDA compared to the PDI molecular counterpart, achieving yields exceeding 90%. Electron property studies and density functional theory calculations show that the PDI-PDA with its well-defined crystal structure, enhances π-π stacking and lowers the electron transition barrier. Moreover, the strong electron-withdrawing ability of the PDI unit promotes the spatial separation of the valency band maximum and conduction band minimum of PDI-PDA suppressing the rapid recombination of photogenerated electron-hole pairs and improving charge separation efficiency to give high photocatalytic efficiency. This study provides a brief yet effective way for the improvement of the photocatalytic efficiency of commonly used PDI-based dyes by integrating them into a framework skeleton.

"One-Stone-Three-Birds" H2S-Photothermal Therapy for Enhanced Thrombolysis and Vascular Healing.

Thrombus causes a serious condition characterized by the formation of blood clots in blood vessels or heart, potentially leading to life-threatening emergencies. Photothermal therapy (PTT) serves as a treatment for thrombosis that provides noninvasive thrombus dissolution and fewer bleeding side effects. However, the high temperatures generated by PTT can exacerbate vascular inflammation and promote thrombus recurrence. In this study, a photothermal hydrogen sulfide (H2S) nanogenerator (PSA@ADT-OH) is constructed using a perylene-cored photothermal agent (PSA) coassembled with a H2S donor ADT-OH. The system PSA@ADT-OH demonstrates outstanding targeting and accumulation efficiency against blood flow shear forces. It also provides sustained H2S release at thrombus sites, contributing to antiplatelet aggregation, reactive oxygen species clearance, and vascular healing. This approach opens up new possibilities for advanced thrombus treatment.

Selenophene-fused Perylene Diimide-Based Cathode Interlayer Enables 19 % Efficiency Binary Organic Solar Cells via Stimulative Charge Extraction.

The cathode interlayer is crucial for the development of organic solar cells (OSCs), but the research on simple and efficient interlayer materials is lagging behind. Here, a donor-acceptor (D-A) typed selenophene-fused perylene diimide (PDI) derivative (SePDI3) is developed as cathode interlayer material (CIM) for OSCs, and a non-fused PDI derivative (PDI3) is used as the control CIM for comparison. Compared to PDI3, SePDI3 shows a stronger self-doping effect and better crystallinity, resulting in better charge transport ability. Furthermore, the interaction between SePDI3 and L8-BO can form an efficient extraction channel, leading to superior charge extraction behavior. Finally, benefitting from significantly enhanced charge transport and extraction capacity, the SePDI3-based device displays a champion PCE of 19.04 % with an ultrahigh fill factor of 81.65 % for binary OSCs based on PM6 : L8-BO active layer, which is one of the top efficiencies reported to date in binary OSCs based novel CIMs. Our work prescribes a facile and effective fusion strategy to develop high-efficiency CIMs for OSCs.

Cation-Dependent Mixed Ionic-Electronic Transport in a Perylenediimide Small-Molecule Semiconductor.

A rapidly growing interest in organic bioelectronic applications has spurred the development of a wide variety of organic mixed ionic-electronic conductors. While these new mixed conductors have enabled the community to interface organic electronics with biological systems and efficiently transduce biological signals (ions) into electronic signals, the current materials selection does not offer sufficient selectivity towards specific ions of biological relevance without the use of auxiliary components such as ion-selective membranes. Here, we present the molecular design of an n-type (electron-transporting) perylene diimide semiconductor material decorated with pendant oligoether groups to facilitate interactions with cations such as Na+ and K+. Using the cyclic 15-crown-5 oligoether motif, we find that the resulting mixed conductor PDI-crown displays a strong dependence on the size of the electrolyte cation when tested in an organic electrochemical transistor configuration. In stark contrast to the low current response on the order of 1 µA observed with aqueous sodium chloride, a nearly 200-fold increase in current is observed with aqueous potassium chloride. We ascribe the high selectivity to extended molecular aggregation and therefore efficient charge transport in the presence of K+ due to a favourable sandwich-like structure between two adjacent 15-crown-5 motifs and the potassium ion.

Excited Charge Transfer Promoted Electron Transfer in all Perylenediimide Derived, Wide-Band Capturing Conjugates: A Mimicry of the Early Events of Natural Photosynthesis.

Fundamental discoveries in electron transfer advance scientific and technological advancements. It is suggested that in plant and bacterial photosynthesis, the primary donor, a chlorophyll or bacteriochlorophyll dimer, forms an initial excited symmetry-breaking charge transfer state (1CT*) upon photoexcitation that subsequently promotes sequential electron transfer (ET) events. This is unlike monomeric photosensitizer-bearing donor-acceptor dyads where ET occurs from the excited donor or acceptor (1D* or 1A*). In the present study, we successfully demonstrated the former photochemical event using an excited charge transfer molecule as a donor. Electron-deficient perylenediimide (PDI) is functionalized with three electron-rich piperidine entities at the bay positions, resulting in a far-red emitting CT molecule (DCT). Further, this molecule is covalently linked to another PDI (APDI) carrying no substituents at the bay positions, resulting in wide-band capturing DCT-APDI conjugates. Selective excitation of the CT band of DCT in these conjugates leads to an initial 1DCT* that undergoes subsequent ET involving APDI, resulting in DCT +-APDI - charge separation product (kCS~109 s-1). Conversely, when APDI was directly excited, ultrafast energy transfer (ENT) from 1APDI* to DCT (kENT~1011 s-1) followed by ET from 1DCT* to PDI is witnessed. While increasing solvent polarity improved kCS rates, for a given solvent, the magnitude of the kCS values was almost the same, irrespective of the excitation wavelengths. The present findings demonstrate ET from an initial CT state to an acceptor is key to understanding the intricate ET events in complex natural and bacterial photosynthetic systems possessing multiple redox- and photoactive entities.

Alkyl-Doping Enables Significant Suppression of Conformational Relaxation and Intermolecular Nonradiative Decay for Improved Near-Infrared Fluorescence Imaging.

Despite various efforts to optimize the near-infrared (NIR) performance of perylene diimide (PDI) derivatives for bio-imaging, convenient and efficient strategies to amplify the fluorescence of PDI derivatives in biological environment and the intrinsic mechanism studies are still lacking. Herein, we propose an alkyl-doping strategy to amplify the fluorescence of PDI derivative-based nanoparticles for improved NIR fluorescence imaging. The developed PDI derivative, OPE-PDI, shows much brighter in n-Hexane (HE) compared with that in other organic media, and the excited state dynamics investigation experimentally elucidates the solvent effect-induced suppression of intermolecular energy transfer and intramolecular nonradiative decay as the underlying mechanism for the fluorescence improvement. Theoretical calculations reveal the lowest reorganization energies of OPE-PDI in HE among various solvents, indicating the effectively suppressed conformational relaxation to support the strongest radiative decay. Inspired by this, an alkyl atmosphere mimicking HE is constructed by incorporating the octadecane into OPE-PDI-based nanoparticles, permitting up to 3-fold fluorescence improvement compared with the counterpart nanoparticles. Owing to the merits of high brightness, anti-photobleaching, and low biotoxicity for the optimal nanoparticles, they have been employed for probing and long-term monitoring of tumor. This work highlights a facile strategy for the fluorescence enhancement of PDI derivative-based nanoparticles.

Self-Assembly Behavior, Aggregation Structure, and the Charge Carrier Transport Properties of S-Heterocyclic Annulated Perylene Diimide Derivatives.

The construction of high-performance n-type semiconductors is crucial for the advancement of organic electronics. As an attractive n-type semiconductor, molecular systems based on perylene diimide derivatives (PDIs) have been extensively investigated over recent years. Owing to the fascinating aggregated structure and high performance, S-heterocyclic annulated PDIs (SPDIs) are receiving increasing attention. However, the relationship between the structure and the electrical properties of SPDIs has not been deeply revealed, restricting the progress of PDI-based organic electronics. Here, we developed two novel SPDIs with linear and dendronized substituents in the imide position, named linear SPDI and dendronized SPDI, respectively. A series of structural and property characterizations indicated that linear SPDI formed a long-range-ordered crystalline structure based on helical supramolecular columns, while dendronized SPDI, with longer alkyl side chains, formed a 3D-ordered crystalline structure at a low temperature, which transformed into a hexagonal columnar liquid crystal structure at a high temperature. Moreover, no significant charge carrier transport signal was examined for linear SPDI, while dendronized SPDI had a charge carrier mobility of 3.5 × 10-3 cm2 V-1 s-1 and 2.1 × 10-3 cm2 V-1 s-1 in the crystalline and liquid crystalline state, respectively. These findings highlight the importance of the structure-function relationship in PDIs, and also offer useful roadmaps for the design of high-performance organic electronics for down-to-earth applications.

Role of Intragap States in Sensitized Sb-Doped Tin Oxide Photoanodes for Solar Fuels Production.

In view of developing photoelectrosynthetic cells which are able to store solar energy in chemical bonds, water splitting is usually the reaction of choice when targeting hydrogen production. However, alternative approaches can be considered, aimed at substituting the anodic reaction of water oxidation with more commercially capitalizable oxidations. Among them, the production of bromine from bromide ions was investigated long back in the 1980s by Texas Instruments. Herein we present optimized perylene-diimide (PDI)-sensitized antimony-doped tin oxide (ATO) photoanodes enabling the photoinduced HBr splitting with >4 mA/cm2 photocurrent densities under 0.1 W/cm2 AM1.5G illumination and 91 ± 3% faradaic efficiencies for bromine production. These remarkable results, among the best currently reported for the photoelectrochemical Br- oxidation by dye sensitized photoanodes, are strongly related to the occupancy extent of ATO's intragap (IG) states, generated upon Sb-doping, as demonstrated by comparing their performances with PDI-sensitized analogues on both undoped SnO2- and TiO2-passivated ATO scaffolds by means of (spectro)electrochemistry and electrochemical impedance spectroscopy. The architecture of the ATO-PDI photoanodic assembly was further modified via the introduction of a molecular iridium-based water oxidation catalyst, thus proving the versatility of the proposed hybrid interfaces as photoanodic platforms for photoinduced oxidations in PEC devices.

A perylene diimide probe for NIR-II fluorescence imaging guided photothermal and type I/type II photodynamic synergistic therapy.

Phototherapy has garnered significant attention in the past decade. Photothermal and photodynamic synergistic therapy combined with NIR fluorescence imaging has been one of the most attractive treatment options because of the deep tissue penetration, high selectivity and excellent therapeutic effect. Benefiting from the superb photometrics and ease of modification, perylene diimide (PDI) and its derivatives have been employed as sensing probes and therapeutic agents in the biological and biomedical research fields, and exhibiting excellent potential. Herein, we reported the development of a novel organic small-molecule phototherapeutic agent, PDI-TN. The absorption of PDI-TN extends into the NIR region, which provides feasibility for NIR phototherapy. PDI-TN overcomes the traditional Aggregation-Caused Quenching (ACQ) effect and exhibits typical characteristics of Aggregation-Induced Emission (AIE). Subsequently, PDI-TN NPs were obtained by using an amphiphilic triblock copolymer F127 to encapsulate PDI-TN. Interestingly, the PDI-TN NPs not only exhibit satisfactory photothermal effects, but also can generate O2•- and 1O2 through type I and type II pathways, respectively. Additionally, the PDI-TN NPs emit strong fluorescence in the NIR-II region, and show outstanding therapeutic potential for in vivo NIR-II fluorescence imaging. To our knowledge, PDI-TN is the first PDI derivative used for NIR-II fluorescence imaging-guided photodynamic and photothermal synergistic therapy, which suggests excellent potential for future biological/biomedical applications.

Fluorescence Turn-on Detection of Perfluorooctanoic Acid (PFOA) by Perylene Diimide-Based Metal-Organic Framework.

A novel, water-stable, perylene diimide (PDI) based metal-organic framework (MOF), namely, U-1, has been synthesized for selective and sensitive detection of perfluorooctanoic acid (PFOA) in mixed aqueous solutions. The MOF shows highly selective fluorescence turn-on detection via the formation of a PFOA-MOF complex. This PFOA-MOF complex formation was confirmed by various spectroscopic techniques. The detection limit of the MOF for PFOA was found to be 1.68 µM in an aqueous suspension. Upon coating onto cellulose paper, the MOF demonstrated a significantly lower detection limit, down to 3.1 nM, which is mainly due to the concentrative effect of solid phase extraction (SPE). This detection limit is lower than the fluorescence sensors based on MOFs previously reported for PFAS detection. The MOF sensor is regenerable and capable of detecting PFOA in drinking and tap water samples. The PDI-MOF-based sensor reported herein represents a novel approach, relying on fluorescence turn-on response, that has not yet been thoroughly investigated for detecting per- and polyfluoroalkyl substances (PFAS) until now.

Ring Fusion Elevates the Electronic Mobility of Azabenzannulated Perylene Diimide.

The backwardness of n-type organic semiconductors still exists compared with the p-type counterparts. Thus, the development of high-performance n-type organic semiconductors is of great importance for organic electronic devices and their integrated circuits. In recent years, azabenzannulated perylene diimide (PDI), as one of immense bay-region-annulated PDI derivatives, has drawn considerable attentions. However, the electronic mobilities of azabenzannulated PDI derivatives are barely satisfactory. In this contribution, the peripheral benzene ring in azabenzannulated PDI 2 was fused to the ortho position by intramolecular C-H arylation cyclization. This endows the resultant azabenzannulated PDI 4 a planar configuration as well as electron deficient pentagonal ring. As a result, the electronic mobility of 4 is almost two orders of magnitude higher than that of the nonfused azabenzannulated PDI 2. This work shall pave a new avenue in elevating the performance of azabenzannulated PDI in organic electronics.

Band-like transport in solution-processed perylene diimide dianion films with high Hall mobility.

It is crucial to prepare high-mobility organic polycrystalline film through solution processing. However, the delocalized carrier transport of polycrystalline films in organic semiconductors has rarely been investigated through Hall-effect measurement. This study presents a strategy for building strong intermolecular interactions to fabricate solution-crystallized p-type perylene diimide (PDI) dianion films with a closer intermolecular π-π stacking distance of 3.25 Å. The highly delocalized carriers enable a competitive Hall mobility of 3 cm2 V-1 s-1, comparable to that of the reported high-mobility organic single crystals. The PDI dianion films exhibit a high electrical conductivity of 17 S cm-1 and typical band-like transport, as evidenced by the negative temperature linear coefficient of mobility proportional to T-3/2. This work demonstrates that, as the intermolecular π-π interactions become strong enough, they will display high mobility and conductivity, providing a new approach to developing high-mobility organic semiconductor materials.

Semi-Transparent Luminescent Solar Concentrators Based on Intramolecular Energy Transfer in Polyurethane Matrices.

Luminescent solar concentrators (LSCs) are spectral conversion devices offering interesting opportunities for the integration of photovoltaics into the built environment and portable systems. The Förster-resonance energy transfer (FRET) process can boost the optical response of LSCs by reducing energy losses typically associated to non-radiative processes occurring within the device under operation. In this work, a new class of FRET-based thin-film LSC devices is presented, in which the synthetic versatility of linear polyurethanes (PU) is exploited to control the photophysical properties and the device performance of the resulting LSCs. A series of luminescent linear PUs are synthesized in the presence of two novel bis-hydroxyl-functionalized luminophores of suitable optical properties, used as chain extenders during the step-growth polyaddition reaction for the formation of the linear macromolecular network. By synthetically tuning their composition, the obtained luminescent PUs can achieve a high energy transfer efficiency (≈90%) between the covalently linked luminophores. The corresponding LSC devices exhibit excellent photonic response, with external and internal photon efficiencies as high as ≈4% and ≈37%, respectively. Furthermore, their optimized power conversion efficiency combined with their enhanced average visible-light transmittance highlight their suitability for potential use as transparent solar energy devices.

Efficient selective aerobic oxidation of sulfides by molecular dipole modulation in methylphosphate-substituted perylene diimide supramolecular polarization photocatalyst.

Photocatalytic aerobic oxidation is a promising sustainable strategy for the selective organic synthesis of industrially valuable chemicals. However, the poor charge separation and insufficient molecular activation restrict the overall photocatalytic efficiency. To address these issues, we have developed a novel approach involving molecular dipole modulation and polar molecular self-assembly to modulate the built-in electric field (BEF) in perylene diimide (PDI) supramolecular polarization photocatalysts by adjusting the electronegativity of terminal substituents. The optimized methylphosphate-substituted PDI (P-PDIP) supramolecular system features the strongest BEF induced by its large molecular dipole, with an intensity 3.89 times higher than that observed in methylcarboxy-substituted PDI (P-PDIC) and 5.64 times higher than that observed in P-PDI. This significant enhancement in BEF generates a powerful driving force within P-PDIP, facilitating directional charge separation toward active sites. Additionally, the incorporation of methylphosphate groups improves the activation efficiency of O2 and thioether molecules, resulting in a remarkable photocatalytic performance for selective aerobic oxidation of sulfides into sulfoxide (up to 99.9% conversion and 99.8% selectivity). This study highlights that enhancing BEF through manipulating molecular dipoles can significantly improve photocatalytic activity, offering great potential for constructing efficient organic polarization photocatalysts in green chemistry and sustainable production.

Self-standing perylene diimide covalent organic framework membranes for trace TMA sensing at room temperature.

The unprecedented demand for highly selective, real-time monitoring and low-power gas sensors used in food quality control has been driven by the increasing popularity of the Internet of Things (IoT). Herein, the self-standing perylene diimide based covalent organic framework membranes (COFMPDI-THSTZ) were prepared via liquid-liquid interfacial synthesis method. By incorporating the perylene diimide monomer into the COFM through molecular engineering, COFMPDI-THSTZ based sensor demonstrated an outstanding trimethylamine (TMA)-sensing performance at room temperature. Benefited from the TMA-accessible self-standing membrane morphology, π-electron delocalization effect, and extensive surface area with continuous nanochannels, the specific and highly sensitive TMA measurement has been achieved within the range of 0.03-400 ppm, with an exceptional theoretical detection limit as low as 10 ppb. Moreover, the primary internal mechanism of COFMPDI-THSTZ for this efficient TMA detection was investigated through in-situ FT-IR spectra, thereby directly elucidating that the chemisorption interaction of oxygen modulated the depletion layers on sensing material surface, resulting in alterations in sensor resistance upon exposure to the target gas. For practical usage, COFMPDI-THSTZ based sensor exhibited exceptional real-time in-situ sensing capabilities, further confirmed their potential for application in dynamic prediction evaluation of marine fish products and quality monitoring in IoT.

Enhancing Pollutant Mineralization through Organic-Inorganic Defect-Transit Dual S-scheme with a Robust Internal Electric Field.

Achieving superior photomineralization of pollutants relies on a rational design of a dual S-scheme with a robust internal electric field (IEF). In this study, to tackle the low mineralization rate in type-II In2 O3 /In2 S3 (IO/IS) systems, an organic-inorganic dual S-scheme In2 O3 /PDI/In2 S3 (IO/PDI/IS) nanostructured photocatalyst is synthesized via a method combining solvent-induced self-assembly and electrostatic forces. Due to the unique energy band position and strong IEF, the photoinduced defect-transit dual S-scheme IO/PDI/IS facilitates the degradation of lignin and antibiotics. Notably, a promising mineralization rate of 80.9% for sodium lignosulfonate (SL) is achieved. The charge transport pathway of IO/PDI/IS are further validated through the analysis of in situ X-ray photoelectron spectroscopy (in situ XPS), density functional theory calculations, and radical trapping experiments. In-depth, two possible pathways for the photocatalytic degradation of lignin are proposed based on the intermediates monitored by liquid chromatography-mass spectrometry (LC-MS). This study presents a new strategy for the design of organic-inorganic dual S-scheme photocatalysts with a robust IEF for pollutant degradation.

Toward Type I/II ROS Generation Photoimmunotherapy by Molecular Engineering of Semiconducting Perylene Diimide.

As prospective phototheranostic agents for cancer imaging and therapy, semiconducting organic molecule-based nanomedicines are developed. However, near-infrared (NIR) emission, and tunable type I (O2 • -) and type II (1O2) photoinduced reactive oxygen species (ROS) generation to boost cancer photoimmunotherapy remains a big challenge. Herein, a series of D-π-A structures, NIR absorbing perylene diimides (PDIs) with heavy atom bromide modification at the bay position of PDIs are prepared for investigating the optimal photoinduced type I/II ROS generation. The heavy atom effect has demonstrated a reduction of molecular ∆EST and promotion of the intersystem crossing processes of PDIs, enhancing the photodynamic therapy (PDT) efficacy. The modification of three bromides and one pyrrolidine at the bay position of PDI (TBDT) has demonstrated the best type I/II PDT performance by batch experiments and theoretical calculations. TBDT based nanoplatforms (TBDT NPs) enable type I/II PDT in the hypoxic tumor microenvironment as a strong immunogenic cell death (ICD) inducer. Moreover, TBDT NPs showing NIR emission allow in vivo bioimaging guided phototherapy of tumor. This work uses novel PDIs with adjustable type I/II ROS production to promote antitumor immune response and accomplish effective tumor eradication, consequently offering molecular guidelines for building high-efficiency ICD inducers.

Full-Spectrum Responsive Naphthalimide/Perylene Diimide with a Giant Internal Electric Field for Photocatalytic Overall Water Splitting.

The co-assembly naphthalimide/perylene diimide (NDINH/PDINH) supramolecular photocatalysts were successfully synthesized via a rapid solution dispersion method. A giant internal electric field (IEF) in co-assembly structure was built by the larger local dipole. NDINH coated on PDINH could reduce the reflected electric field over PDINH to improve its responsive activity to ultraviolet light. Resultantly, an efficient full-spectrum photocatalytic overall water splitting activity with H2 and O2 evolution rate of 317.2 and 154.8 µmol g-1 h-1 for NDINH/PDINH together with optimized O2 evolution rate with 2.61 mmol g-1 h-1 using AgNO3 as a sacrificial reagent were achieved. Meanwhile, its solar-to-hydrogen efficiency was enhanced to 0.13 %. The enhanced photocatalytic activity was primarily attributed to the IEF between NDINH and PDINH, significantly accelerating transfer and separation of photogenerated carriers. Additionally, a direct Z-Scheme pathway of carriers contributed to a high redox potential. The strategy provided a new perspective for the design of supramolecular photocatalysts.