Donor-acceptor Systems Research Articles

Long organic persistent luminescence triggered by photo-induced charge-separation for water-resistant information encryption.

The long persistent luminescence (LPL) phenomenon in the water environment presents us with a broad blueprint to struggle for a new generation of optical materials. However, the realization of water-resistant LPL remains a formidable challenge due to severe quenching of triplet excitons inflowing media. Here, an electron donor-acceptor system is designed based on a B2O3 host and carbon dot (CD) guest, which exhibits deep-blue LPL with a lasting time of about 21 s to the naked eye. The average LPL lifetime is over 2 s, and the LPL quantum yield is 10.78%. This host-guest system possesses charge-separated states and charge-transferred states triggered by an optical source, which is the foundation for LPL. Importantly, in water environments (HCl, NaOH, electrolyte NaCl, and H2O), the LPL of as-obtained CDs@B2O3 can still remain due to high environmental stability of B2O3. Based on the excellent LPL with ultra-long lifetime and water-resistant feature, the CDs@B2O3 successfully applies in water-resistant information encryption.

Construction of Covalent Triazine Frameworks with Electronic Donor-Acceptor System for Efficient Photocatalytic C-H Hydroxylation of Imidazole[1,2-α]Pyridine Derivatives.

Covalent triazine frameworks (CTFs) are promising heterogeneous photocatalyst candidates owing to their excellent stability, conjugacy, and tunability. In this study, a series of CTFs decorated with different substituents (H, MeO, and F) were synthesised and utilised as photocatalysts for C-H activation reactions. The corresponding optoelectronic properties could be precisely regulated by the electronic effects of different substituents in the nanopore channels of the CTFs; these CTFs were effective photocatalysts for C-H activation in organic synthesis due to their unique structures and optoelectronic properties. Methoxy-substituted CTF (MeO-CTF) exhibited extraordinary catalytic performance and reusability in C-H functionalization by constructing an electronic donor-acceptor system, achieving the highest yield in the photocatalytic C3-H hydroxylation of 2-phenylimidazole[1,2-α]pyridine. This strategy provides a new scaffold for the rational design of CTFs as efficient photocatalysts for organic synthesis.

Exploring Through-Space Charge Transfer-Mediated Optoelectrochemical Properties of Dual-State Luminescent Aliphatic Polymers and Optoelectronic Responses toward Metal Ions.

Herein, natural-synthetic hybrid dual-state luminescent conducting polymers (DLCPs/DLCP1-DLCP8) possessing significant optoelectrochemical properties are strategically developed by the polymerization of prop-2-enamide, cis-butenedioic acid, 2-acrylamido-2-methylpropane-1-sulfonic acid, and in situ-generated 2-(3-acrylamidopropanamido)-2-methylpropane-1-sulfonic acid alongside the grafting of gum tragacanth. The spectroscopic data of aliphatic DLCPs affirm DLCP7 as the most stable supramolecular assembly endowing optoelectronic properties. Computational calculations identified -C(═O)NH-, -C(═O)OH, -OH, and -SO3H as subluminophores. The absorption spectra, excitation wavelength-/solvent-polarity-/concentration-dependent luminescence, solid state luminescence, aggregation-induced enhanced luminescence, and time-correlated single photon count (TCSPC) studies confirm the occurrence of aggregation-mediated intramolecular through-space charge transfer (ITSCT) in the excited state of DLCP7. Mulliken charge, natural bond orbital, dipole moments, and electronic potential surface analyses confirm the charge donor-acceptor system in DLCP7. Furthermore, the selective optoelectronic response of DLCP7 toward Ca2+/Cu(II) at 438/574 nm is explored using ultraviolet-visible spectra, TCSPC analyses, a dynamic light scattering study, and computational investigations. The chelation-enhanced luminescence and ITSCT inhibition are responsible for turn-on and turn-off detections of Ca2+ and Cu(II), respectively. Cu(II) → Cu(I) reduction in a DLCP7 solution is inferred from electrochemical and spectroscopic analyses. The conductivities of 9.65 × 10-5 S cm-1 (solid state) and 44.35 × 10-5 S cm-1 (solution) in DLCP7 are validated by current-voltage and electrochemical impedance measurements. Again, strong electronic conductivities of 43.89 × 10-5 S cm-1 (solid state)/53.34 × 10-5 S cm-1 (solution) and 45.42 × 10-5 S cm-1 (solid state)/64.81 × 10-5 S cm-1 (solution) are observed in Ca2+-DLCP7 and Cu(II)-DLCP7, respectively.

Construction of 0-dimensional silver quantum dot/MoSe2@MXene/3-dimensional porous copper foam composite electrodes with heterogeneous interfaces for synergistic electrocatalytic degradation of antibiotics

This study proposes a novel and efficient Ag quantum dots (QDs)/MoSe2@two-dimensional transition metal carbide/nitride (MXene)/copper foam (CF) composite electrode to address the challenge of electrocatalytic degradation of antibiotics in water. The electrode formed a unique electron donor–acceptor system by loading Ag QDs and heterostructured nanosheets on CF, significantly facilitating charge transfer and segregation at the interface. The catalytically active sites at the edges and defective locations of MoSe2 in conjunction with the two-dimensional MXene structure, which formed an efficient electron transfer channel, promoted the electron transfer from the interior to the surface and accelerated the hydrogen adsorption and reduction reactions. Moreover, the charge redistribution at the interface of Ag QDs and MoSe2@MXene formed interfacial dipoles, increasing the active sites on the catalyst surface and promoting the generation of cathodic atomic hydrogen (H*). Under optimal conditions, the degradation rate of tigecycline (TGC) reached as high as 90.1 % ± 2.4 % within 60 min. The anode-generated OH and HClO, along with the cathode-generated H, further promoted the degradation of TGC through co-catalysis. The degradation pathways were analyzed using density-functional theory (DFT) calculations and liquid chromatography-mass spectrometry (LC-MS) techniques. Moreover, toxicity analysis of the degradation products was carried out to ensure the safety of the treated wastewater discharge. A reflux continuous effluent reactor was also designed to achieve high degradation efficiency and low energy consumption after stable operation, laying the foundation for industrial applications. This technology provides new ideas for the design of green, efficient, stable, and low-consumption electrocatalytic reactors and contributes to a sustainable future environment.

Constructing Donor–Acceptor-Linked COFs Electrolytes to Regulate Electron Density and Accelerate the Li+ Migration in Quasi-Solid-State Battery

HighlightsDonor–acceptor-linked covalent organic framework (COF)-based electrolyte can not only fulfill highly-selective Li+ conduction, but also offer a crucial opportunity to understand the role of electronic density in quasi-solid-state Li metal batteries.Donor–acceptor-linked COF electrolyte results in Li+ transference number 0.83, high ionic conductivity 6.7 × 10–4 S cm−1 and excellent cyclic ability in Li metal batteries.In situ characterizations, density functional theory calculation and time-of-flight secondary ion mass spectrometry are adopted to expound the mechanism of the rapid migration of Li+ in the “donor–acceptor” electrolyte system.

Inverse Design of Singlet-Fission Materials with Uncertainty-Controlled Genetic Optimization.

Singlet fission has shown potential for boosting the efficiency of solar cells, but the scarcity of suitable molecular materials hinders its implementation. We introduce an uncertainty-controlled genetic algorithm (ucGA) based on ensemble machine learning predictions from different molecular representations that concurrently optimizes excited state energies, synthesizability, and exciton size for the discovery of singlet fission materials. The ucGA allows us to efficiently explore the chemical space spanned by the reFORMED fragment database, which consists of 45,000 cores and 5,000 substituents derived from crystallographic structures assembled in the FORMED repository. Running the ucGA in an exploitative setup performs local optimization on variations of known singlet fission scaffolds, such as acenes. In an explorative mode, hitherto unknown candidates displaying excellent excited state properties for singlet fission are generated. We suggest a class of heteroatom-rich mesoionic compounds as acceptors for charge-transfer mediated singlet fission. When included in larger donor-acceptor systems, these units exhibit localization of the triplet state, favorable diradicaloid character and suitable triplet energies for exciton injection into semiconductor solar cells.

Four compounds containing 1-(2-carboxyethyl)-4,4′-bipyridine: Synthesis, crystal structure and chromic behavior

Herein, four compounds containing the neutral viologen derivative, 1-(2-carboxyethyl)-4,4′-bipyridine (CBbpy) have been synthesized, (CBbpy)·(H2TPDC)·H2O (1), [Co0.5(CBbpy)(H2O)2](HTPDC)·2 H2O (2), [Ni0.5(CBbpy)(H2O)2](HTPDC)·2 H2O (3) and {[Cd(CBbpy)2(H2O)2][Cd(TPDC)2]·4 H2O}n (4) (H2TPDC = thiophene-2,5-dicarboxylic acid). Compound 1 is a co-crystal that forms the donor-acceptor (D-A) system through non-covalent interactions. Compounds 2 and 3 own the same isolated structure, in which metal ions coordinate with CBbpy to form cations, while H2TPDC loses a proton to form anions. Compound 4 contains one-dimensional (1D) {[Cd(CBbpy)2(H2O)2]2+}n double chain and two-dimensional (2D) {[Cd(TPDC)2]2-}n layer, which leads to a 1D + 2D→three-dimensional (3D) interdigitated supramolecular architecture. Although four compounds comprise the same bipyridinium moiety, their chromic behaviors are different. Compounds 1 and 4 own reversible photochromic action, while 2 and 3 reveal hydrochromic action upon heating. Based on the photochromic properties of 1 and 4, the photo-modulated fluorescence and the potential applications of inkless and erasable printing are investigated.

Tetrazole and Oxadiazole Derivatives as Thermally Activated Delayed Fluorescence Emitters.

Organic light-emitting diodes (OLEDs) are promising lighting solutions for sustainability and energy efficiency. Incorporating thermally activated delayed fluorescence (TADF) molecules enables OLEDs to achieve internal quantum efficiency (IQE), in principle, up to 100 %; therefore, new classes of promising TADF emitters and modifications of existing ones are sought after. This study explores the TADF emission properties of six designed TADF emitters, examining their photophysical responses using experimental and theoretical methods. The design strategy involves creating six distinct types of a donor-acceptor (D-A) system, where tert-butylcarbazoles are used as donors, while the acceptor component incorporates three different functional groups: nitrile, tetrazole and oxadiazole, with varying electron-withdrawing character. Additionally, the donor-acceptor distance is adjusted using a phenylene spacer, and its influence on TADF functionality is examined. The clear dependency of an additional spacer, inhibiting TADF, could be revealed. Emitters with a direct donor-acceptor connection are demonstrated to exhibit TADF moderate emissive behavior. The analysis emphasizes the impact of charge transfer, singlet-triplet energy gaps (ΔEST), and other microscopic parameters on photophysical rates, permitting TADF. Among the emitters, TCz-CN shows optimal performance as a blue-green emitter with an 88 % photoluminescence quantum yield (PLQY) and fast rate of reversible intersystem crossing of 2×106 s-1 and 1×107 s-1, obtained from time-resolved photoluminescence (TRPL) experiment in PMMA matrix and quantum mechanical calculations, respectively. This comprehensive exploration identifies molecular bases of superior TADF emitters and provides insights for future designs, advancing the optimization of TADF properties in OLEDs.

Heavy-Atom-Free Covalent Organic Frameworks for Organic Room-Temperature Phosphorescence via Förster and Dexter Energy Transfer Mechanism.

Covalent organic frameworks (COFs), with their accessible nanoscale porosity, selectable building blocks, and precisely engineered topology, offer unique benefits in the design of room-temperature phosphorescent (RTP) materials. However, their potential has been limited by phosphorescence quenching caused by interlayer π-π stacking interactions. This paper presents a novel strategy to enhance RTP in heavy-atom-free COFs by employing a donor-acceptor (D-A) system that leverages the Förster resonance energy transfer (FRET) and Dexter energy transfer (DET) mechanisms. Among the materials investigated, the best-performing COF exhibits a phosphorescence lifetime of 4.35ms at room temperature. Spectral analysis, structural analysis, and theoretical calculations indicate the presence of intralayer FRET processes as well as interlayer DET processes within the D-A COF system. Potential anti-counterfeiting applications are explored by exploiting the unique phosphorescent properties of these materials. Additionally, the inherent permanent porosity of COFs presents new opportunities for future development and application. This strategy offers many promising prospects for advancing the RTP technology in COF materials and broadens their potential applications in various fields.

Rational Design of 3D Space Connected Donor–Acceptor System in Covalent Organic Frameworks for Enhanced Photocatalytic Performance

AbstractHerein, a rational strategy is presented to reduce the energy barrier of singlet ground state to singlet excited state transitions, whilst simultaneously reducing energy losses in populating triplet excited states. The approach relies on constructing 3D space connected donor–acceptor systems in COFs. The 3D space connected D–A system in 8‐connected 3D COFs (denoted as COF‐1 and COF‐2) allows the efficient transfer of electrons, overcoming the traditional electron transport limitations of 2D COFs and significantly boosting the solar energy utilization efficiency under visible light irradiation. COF‐2, possessing an extended π‐conjugated structure relative to COF‐1, demonstrated high selectivity for the photocatalytic generation of H2O2 (6.93 mmol g−1 h−1) in natural seawater without the need for sacrificial reagents, exceeding the performance of most previously reported COF‐based photocatalysts. The 3D space connected D–A system reported in this work offers a new approach for optimizing electron and energy transfer in COF‐based photocatalysts for H2O2 production and other applications.

Excited-State Dynamics in Segregated Donor-Acceptor Stacks Versus a Peri-Bisdonor-Acceptor System.

The investigation of impact of through-space/through-bond electronic interaction among chromophores on photoexcited-state properties has immense potential owing to the distinct emergent photophysical pathways. Herein, the photoexcited-state dynamics of homo-sorted π-stacked aggregates of a naphthalenemonoimide and perylene-based acceptor-donor (NI-Pe) system and a fork-shaped acceptor-bisdonor (NI-Pe2) system possessing integrally stacked peri-substituted donors was examined. Femtosecond transient absorption (fsTA) spectra of NI-Pe monomer recorded in chloroform displayed spectroscopic signatures of the singlet state of Pe; 1Pe*, the charge-separated state; NI-⋅-Pe+⋅, and the triplet state of Pe; 3Pe*. The examination of ultrafast excited-state processes of NI-Pe aggregate in chloroform revealed faster charge recombination ( =1.75 ns) than the corresponding monomer ( =2.46 ns) which was followed by observation of a broad structureless band attributed to an excimer-like state. The fork-shaped NI-Pe2 displayed characteristic spectroscopic features of the NI radical anion (λmax~450 nm) and perylene dimer radical cation (λmax~520 nm) upon photoexcitation in non-polar toluene solvent in the nanosecond transient absorption (nsTA) spectroscopy. The investigation highlights the significance of intrinsic close-stacked arrangement of donors in ensuring a long-lived photoinduced charge-separated state ( =1.35 μs) in non-polar solvents via delocalization of radical cation between the donors.

In Situ growth of high-crystallinity MOF@CTF core-shell hybrid heterostructures and their application in photoelectrochemical sensing of vancomycin

Vancomycin is a first-line drug for the treatment of methicillin-resistant Staphylococcus aureus (MRSA) and multidrug-resistant bacterial infections. It is of great significance to develop rapid detection methods for vancomycin in different matrices. In this work, a novel method for the in-situ preparation of MOF@CTF core-shell hybrid heterogeneous structures was proposed and applied to the photoelectrochemical detection of vancomycin. The insolubility of the imine precursor structure in homogeneous solvents and the Lewis acidic centers in the MOF structure induced the initial arrangement of CTF on the surface of PCN-224. By encapsulating a layer of highly crystalline CTF structure onto the initial morphology of PCN-224, a MOF@CTF heterogeneous structure was formed. Importantly, the introduction of anthracene-based electron-donating groups into the CTF structure and the formation of a donor-acceptor system with triazine rings enhanced the photoconversion efficiency of the heterogeneous structure by establishing a continuous separated built-in electric field within the core-shell structure. The successful in-situ synthesis of the core-shell hybrid heterogeneous structure was confirmed through microscopic morphology, PXRD, XPS, and FT-IR. Furthermore, investigations into the semiconductor properties of the heterogeneous structure, including semiconductor type, bandgap, and photo-voltage, were conducted. Results showed that the heterogeneous structure exhibited a doubled photocurrent density compared to the original PCN-224. Additionally, a molecularly imprinted photoelectrochemical sensor (MIPECS) for vancomycin was constructed. Under optimized conditions, the sensor demonstrated a superior concentration response range (0.1 nM - 1 μM) and detection limit (0.031 nM, 3σ/S, n = 11). Simultaneously, the potential applicability of the sensor in animal-derived foods, serum, and environmental water samples was evaluated, yielding satisfactory results.

Theoretical model of donor–donor and donor–acceptor energy transfer on a nanosphere

In this study, we introduce a novel advancement in the field of theoretical exploration. Specifically, we investigate the transfer and trapping of electronic excitations within a two-component disordered system confined to a finite volume. The implications of our research extend to energy transfer phenomena on spherical nanoparticles, characterized by randomly distributed donors and acceptors on their surface. Utilizing the three-body Padé approximant technique, previously employed in single-component systems, we apply it to address the challenge of trapping within our system. To validate the robustness of our model, we conduct Monte Carlo simulations on a donor–acceptor system positioned on a spherical nanoparticle. In particular, very good agreement between the model and Monte Carlo simulations has been found for donor fluorescence intensity decay.

Integrating Molecular Motions in Ternary Cocrystals for NIR‐II Photothermal Conversion

Organic photothermal conversion materials hold immense promise for various applications owing to their structural flexibility. Recent research has focused on enhancing near‐infrared (NIR) absorption and mitigating radiative transition processes. In this study, we have developed a viable approach to the design of photothermal conversion materials through the construction of ternary organic cocrystals, by introducing a third component as a molecular blocker and motion unit into a binary donor–acceptor system. Superstructural and photophysical properties of the ternary cocrystals were characterized using various spectroscopic techniques. The role of the molecular blocker in radical stabilization and photothermal conversion were demonstrated. Intriguingly, the motions of the entire pyrene molecules in the cocrystal have been observed by variable temperature single‐crystal X‐ray diffraction results. The excellent performance of ternary cocrystal as a photothermal material was validated through efficient NIR‐II photothermal and solar‐driven water evaporation experiments. The efficiency of water evaporation reached 88.7 %, with a corresponding evaporation rate of 1.29 kg m−2 h−1, representing excellent performance among pure organic small molecular photothermal conversion materials. Our research underscores the introduction of molecular blockers and motion units to stabilize radicals and produce outstanding photothermal conversion materials, offering new pathways for developing efficient and stable photothermal conversion materials.

Integrating Molecular Motions in Ternary Cocrystals for NIR-II Photothermal Conversion.

Organic photothermal conversion materials hold immense promise for various applications owing to their structural flexibility. Recent research has focused on enhancing near-infrared (NIR) absorption and mitigating radiative transition processes. In this study, we have developed a viable approach to the design of photothermal conversion materials through the construction of ternary organic cocrystals, by introducing a third component as a molecular blocker and motion unit into a binary donor-acceptor system. Superstructural and photophysical properties of the ternary cocrystals were characterized using various spectroscopic techniques. The role of the molecular blocker in radical stabilization and photothermal conversion was demonstrated. Intriguingly, the motions of the entire pyrene molecules in the cocrystal have been observed by the results of variable temperature single-crystal X-ray diffraction. The excellent performance of the ternary cocrystal as a photothermal material was validated through efficient NIR-II photothermal and solar-driven water evaporation experiments. The efficiency of water evaporation reached 88.7 %, with a corresponding evaporation rate of 1.29 kg m-2 h-1, representing excellent performance among pure organic small molecular photothermal conversion materials. Our research underscores the introduction of molecular blockers and motion units to stabilize radicals and produce outstanding photothermal conversion materials, offering new pathways for developing efficient and stable photothermal conversion materials.

(Invited) Molecular Donor-Acceptor Systems Derived from Aromatic Heterocycle-Fused Porphyrins

Photoinduced charge separation (CS) in molecular donor-acceptor (D-A) systems is crucial for achieving efficient solar energy conversion in various applications. Despite significant efforts to develop molecular D-A systems over the past decades, it remains a challenge to bring the lifetime of the charge separation state to ms range, which is much shorter than the CS lifetime (~1 s) in natural photosynthetic systems. In this talk, a donor-acceptor system with long-lived charge-separation state (37.2 μs) will be presented. This donor-acceptor system was derived from π-extended porphyrins fused with aromatic heterocycles. Porphyrins fused with aromatic heterocycles represent one fascinating yet very challenging frontiers in chemistry and materials science.1-4 The Wang group has been engaged in developing concise and versatile synthetic and functionalization methods for π-extended porphyrins. The availability of these methods offers easy access to many π-extended porphyrins with novel functionalities.5-7 In this talk, the synthesis, characterization, and the optical and photophysical properties of π-extended porphyrins fused with 5-, 6, and 7-membered rings including 12H-benzo[f]benzo[4,5]imidazo[2,1-a]isoindole and 1,10-phenanthroline, porphyrins will also be presented. Reference Stepien, E. Gonka, M. Zyla and N. Sprutta, Chem. Rev., 2017, 117, 3479-3716.Narita, X. Y. Wang, X. Feng and K. Mullen, Chem. Soc. Rev., 2015, 44, 6616-6643.P. Lewtak and D. T. Gryko, Chem. Commun., 2012, 48, 10069-10086.K. S. Davis, A. L. Thompson and H. L. Anderson, J. Am. Chem. Soc., 2011, 133, 30-3.Hu, M. B. Thomas, W. A. Webre, A. Moss, R. G. W. Jinadasa, V. N. Nesterov, F. D’Souza and H. Wang, Angew. Chem. Int. Ed., 2020, 45 (132), 20250-20257.Moss, Y. Jang, J. Arvidson, V. N. Nesterov, F. D’Souza and H. Wang, Chem. Sci., 2022, 13, 9880 -9890.Moss, D. E. Nevonen, Y. Hu, V. N. Nesterov, V. Nemykin and H. Wang*, ACS Phys. Chem. Au, 2022, 2, 6, 468-481.

Photoexcited States Dynamics on Cu(II) Porphyrines-Nanographenes Dyads

Donor-acceptor systems have garnered significant attention in the fields of semiconducting materials and light harvesting.1 Particularly intriguing are porphyrin diads, wherein porphyrins are covalently bonded to nanographenes, forming a dyad with an expected electron transfer from the porphyrin to the nanographene. In our study, we leverage the excellent charge transport properties of Hexabenzocoronene (HBC) in combination with the superior light harvesting capabilities of Cu(II) porphyrins.The steady-state absorption spectra of the dyads exhibit a linear combination of HBC and porphyrin spectra, suggesting a low degree of electronic coupling in the ground state. Femtosecond optical transient absorption spectroscopy (TAS) has been employed to investigate the dynamics of photoexcited states. The TAS spectrum of the dyad displays a first derivative shape of the steady-state absorption, indicative of a photoinduced electron transfer within the system.2 These findings underscore the potential application of these systems as donor-acceptor systems, wherein the Cu(II) porphyrine serves as the source, transferring electrons to the HBC nanographene. This points towards promising applications of this system in photovoltaic devices. Figure 1. A) Cu(II) porphyrine B) Cu (II) porphyrine, HBC and Cu(II) porphyrine-HBC dyad absorption spectra C) Cu (II) porphyrine with C-H chains, HBC and Cu(II) porphyrinewith C-H chains-HBC dyad absorption spectra D)u (II) porphyrine with C-H chains.______________________________________________[1] H. Imahori, T. Umevama, Journal of Physical Chemistry C 2009, 113, 9029–9039.[2] Shengqiang Xiao; Mohamed E. El-Khouly; Yuliang Li; Zhenhai Gan; Huibiao Liu; Li Jiang; Yasuyuki Araki; Osamu Ito; Daoben Zhu J. Phys. Chem. B 2005, 109, 8, 3658–3667 Figure 1

Balancing TADF Properties in π-Bridged Donor–Acceptor Systems by Sterical Constraints: The Best of Three Worlds

Balancing TADF Properties in π-Bridged Donor–Acceptor Systems by Sterical Constraints: The Best of Three Worlds

Advancing Electrically Conductive Metal-Organic Frameworks for Photocatalytic Energy Conversion.

ConspectusPhotocatalytic energy conversion is a pivotal process for harnessing solar energy to produce chemicals and presents a sustainable alternative to fossil fuels. Key strategies to enhance photocatalytic efficiency include facilitating mass transport and reactant adsorption, improving light absorption, and promoting electron and hole separation to suppress electron-hole recombination. This Account delves into the potential advantages of electrically conductive metal-organic frameworks (EC-MOFs) in photocatalytic energy conversion and examines how manipulating electronic structures and controlling morphology and defects affect their unique properties, potentially impacting photocatalytic efficiency and selectivity. Moreover, with a proof-of-concept study of photocatalytic hydrogen peroxide production by manipulating the EC-MOF's electronic structure, we highlight the potential of the strategies outlined in this Account.EC-MOFs not only possess porosity and surface areas like conventional MOFs, but exhibit electronic conductivity through d-p conjugation between ligands and metal nodes, enabling effective charge transport. Their narrow band gaps also allow for visible light absorption, making them promising candidates for efficient photocatalysts. In EC-MOFs, the modular design of metal nodes and ligands allows fine-tuning of both the electronic structure and physical properties, including controlling the particle morphology, which is essential for optimizing band positions and improving charge transport to achieve efficient and selective photocatalytic energy conversion.Despite their potential as photocatalysts, modulating the electronic structure or controlling the morphology of EC-MOFs is nontrivial, as their fast growth kinetics make them prone to defect formation, impacting mass and charge transport. To fully leverage the photocatalytic potential of EC-MOFs, we discuss our group's efforts to manipulate their electronic structures and develop effective synthetic strategies for morphology control and defect healing. For tuning electronic structures, diversifying the combinations of metals and linkers available for EC-MOF synthesis has been explored. Next, we suggest that synthesizing ligand-based solid solutions will enable continuous tuning of the band positions, demonstrating the potential to distinguish between photocatalytic reactions with similar redox potentials. Lastly, we present incorporating a donor-acceptor system in an EC-MOF to spatially separate photogenerated carriers, which could suppress electron-hole recombination. As a synthetic strategy for morphology control, we demonstrated that electrosynthesis can modify particle morphology, enhancing electrochemical surface area, which will be beneficial for reactant adsorption. Finally, we suggest a defect healing strategy that will enhance charge transport by reducing charge traps on defects, potentially improving the photocatalytic efficiency.Our vision in this Account is to introduce EC-MOFs as an efficient platform for photocatalytic energy conversion. Although EC-MOFs are a new class of semiconductor materials and have not been extensively studied for photocatalytic energy conversion, their inherent light absorption and electron transport properties indicate significant photocatalytic potential. We envision that employing modular molecular design to control electronic structures and applying effective synthetic strategies to customize morphology and defect repair can promote charge separation, electron transfer to potential reactants, and mass transport to realize high selectivity and efficiency in EC-MOF-based photocatalysts. This effort not only lays the foundation for the rational design and synthesis of EC-MOFs, but has the potential to advance their use in photocatalytic energy conversion.

Dihedral Angles and Photoluminescence Quantum Yields: An NMR Analysis.

The synthesis of two different series of donor-acceptor (D-A) molecules is reported, consisting of a series of four structurally related donors and two different acceptors. The subtle differences in the electron density of these D-A-D and D-A compounds are clearly reflected in the different chemical shifts of certain donor protons in the 1H NMR spectra. These shifts show a cosine squared correlation of the dihedral angle between the donor units and the neighbouring phenyl unit of the acceptor. This correlation is also related to optical properties such as the photoluminescence quantum yield, which shows a similar trend due to the different degree of charge transfer during excitation and relaxation processes. In this way, it is possible to directly correlate a molecular structural parameter with a material property on a purely experimental basis, which should be applicable to many donor-acceptor systems.