Reorganization Energy Research Articles

The Mechanism of Redox-Mediated Li2O2 Oxidation and 1O2 Evolution in Li-Air Batteries

The lithium-air (Li-O2) battery has the highest theoretical energy density (3500 Wh kg-1) of any rechargeable battery. Modelling has suggested more than 600 Wh kg-1 may be possible for the whole system, including air handling, making Li-O2 attractive for the electrification of aviation.(1) However, the development of the Li-O2 battery has faced many challenges since its inception, such as degradation and slow kinetics.(2) The discharge product at the cathode is Li2O2, which is electronically insulating and difficult to oxidise on re-charging.(3) To overcome the difficulties of direct electrochemical reactions involving an insulating solid, redox mediating molecules (RMs) were introduced such that the Li2O2 is formed and oxidised in the electrolyte solution in the pores of the cathode.(4) On charging the cell, the RM is oxidised at the surface of the cathode, and then diffuses to and oxidises Li2O2 within the cathode pores, releasing O2. It is desirable for the RM to operate at as low a voltage as possible, above the thermodynamic oxidation potential of Li2O2, to maximise energy efficiency during cycling.In our recent work, we have investigated the mechanism by which RMs oxidise Li2O2 particles.(5) The trend of oxidation rate with mediator potential follows Marcus theory with a maximum rate at +3.74 V. We show that following the initial outer-sphere one-electron oxidation of Li2O2, the dominant subsequent step is the disproportionation of LiO2 to 3O2, and not the one-electron oxidation of LiO2 to 1O2 or 3O2 (Fig. 1). We also show how RMs with different potentials affect the 1O2 yield and that this does not correlate well with degradation, casting doubt on whether 1O2 is the major source of degradation during charge. Our mechanism not only explains why the current generation of mediators cannot deliver high charging rates at sufficiently low potentials for good round-trip energy efficiency but also points the way to designing mediators that can deliver high rates at low charge voltages. W. J. Kwak, et al., Chem Rev, 2020, 120, 6626-6683. S. A. Freunberger, et al., Angew Chem Int Ed Engl, 2011, 50, 8609-8613. V. Viswanathan, et al., J Chem Phys, 2011, 135, 214704. Y. Chen, et al., Nat Chem, 2013, 5, 489-494. S. Ahn, et al., Nat Chem, 2023, 15, 1022-1029. Figure 1

(Invited) Tunable Electronic Charge Transport in Hexammineruthenium Hexacyanometallate Double-Complex Crystals and Their Prussian Blue Analog Thermal Decomposition Products

The complex ions, hexammineruthenium [Ru(NH3)6]2+/3+ and hexacyanoferrate [Fe(CN)6]3-/4- are well known redox couples with reversible interfacial electron transfer kinetics, with rate constants that are too fast to measure with conventional electrochemical methods. This presentation will show that when mixed together, they form insoluble double-complex Ax[Ru(NH3)6][Fe(CN)6] crystals with rhombahedral symmetry, where A is a cationic species and 0≤x≤2. The analogous reaction of [Ru(NH3)6]2+/3+ with [Ru(CN)6]3-/4- produces Ax[Ru(NH3)6][Ru(CN)6] crystals. These materials thus provide an excellent model system to link outer-sphere molecular charge transfer theory with solid-state electronic charge transport. Thermal decomposition at mild temperatures removes ammine ligands and transforms these crystals into nanopolycrystalline/amorphous Prussian blue analogs (PBAs) that retain the macroscopic geometry of the double-complex crystals. This presentation will introduce the crystal structures, spectroscopic characterizations, and electronic charge transport measurements of the double-complex single-crystals and their PBA decomposition products prepared at different oxidation states, including mixed valence forms. Efforts to develop physical models based on density functional theory and Marcus theory to elucidate charge transport in double-complex crystals and PBAs will also be discussed, as well as methods to fabricate neuromorphic devices based on the tunable conductivity of the double-complex crystals and PBAs.

Origins of Narrowband Emission in Nitrogen/Carbonyl Multiresonance Thermally Activated Delayed Fluorescence Emitters: Steric Locks and Vibrational Coupling Effects.

The incorporation of tert-butyl groups and spiro-functionalization into C═O/N-embedded multiresonance thermally activated delayed fluorescence (MR-TADF) systems has yielded materials with superior narrowband emission and excellent color purity. To elucidate the mechanisms underlying the enhanced properties, we present a theoretical study of a series of fused nitrogen/carbonyl derivatives with narrower emission profiles. The key steric factors that contribute to narrowband emission were identified through energy decomposition analysis, induced by structural relaxation in states S0 and S1. Additionally, we achieved potential narrower-band and deep-blue emission by targeting the suppression of vibrational coupling effects. This work provides compelling evidence that a 1-tert-butyl substitution, acting as an end lock, offers minimal reorganization energy and optimal structural stability when combined with a fused lock. Furthermore, new compounds such as 1tBuCZQ and 1tBuDQAO have been identified as promising MR-TADF emitters, delivering ultranarrowband emission as high-quality organic light-emitting diodes.

Computational Studies of the Optoelectronic and Charge Transport Properties of Porphyrin and Corrole‐Based Molecules

ABSTRACTThe structural, optoelectronic and charge transport properties of porphyrin and its analogues are investigated using the density functional theoretical methods. Most of the above molecules absorb in visible region with high light harvesting efficiency. The small energy gap between the frontier molecular orbitals (FMOs) suggests that porphyrin and its derivatives can be used in organic semiconductors. Electronic properties such as ionization potential, electron affinity, reorganization energy and the charge transfer integral are calculated to obtain their charge transport properties. It is revealed that porphyrin, porphyrazine and phthalocyanine act as hole transporters, whereas corrole and corrolazine act as electron transporters.

Heterojunction Organic Solar Cells with Efficient Charge Mobility and Separation Capabilities Studied by DFT.

The properties of the active layer materials play a decisive role in determining the power conversion efficiency of organic solar cells (OSCs). Chlorophyll and its derivatives are abundant and environmentally friendly functional organic molecular materials. Using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), we have calculated the absorption spectra and their excited state properties based on optimized ground state structures. It was found that bacteriochlorin exhibits superior structural properties, a smaller energy gap and hole reorganization energy, redshifted absorption spectra, and higher hole mobility compared to the donor D18. This suggests that bacteriochlorin exhibits superior donor properties. Comparative studies between o-AT-2Cl and m-AT-2Cl showed that o-AT-2Cl had superior acceptor properties, implying that differences in substitution positions can influence the physicochemical properties of non-fullerene acceptors (NFAs). Subsequently, six bulk heterojunctions (BHJs) were constructed by combining three donors with nonfused ring electron acceptors, o-AT-2Cl and m-AT-2Cl. The bacteriochlorin-based BHJs performed well among them, with BChl3/o-AT-2Cl and BChl4/o-AT-2Cl having the largest interfacial charge separation rate. The results suggested that BHJs composed of bacteriochlorin and NFAs can improve OSCs' photovoltaic performance, providing a feasible scheme for designing efficient OSCs.

Understanding and Controlling the Formation of Nonradiative Defects in Blue Organic Triplet Emitters

Phosphorescent organic light-emitting devices (PHOLEDs) suffer from destructive molecular processes due to triplet-polaron and triplet-triplet annihilation. These processes are energetically driven and hence are particularly active in decreasing the lifetime of blue PHOLEDs. It has recently been shown that increasing triplet radiative rates via the Purcell effect effectively extends the device operational lifetime by reducing the triplet radiative lifetime, thus decreasing their density and the probability of triplet-annihilation reactions. We provide an analytical framework using Marcus theory to explain the observed, approximately exponential relationship between exciton energy and device lifetime. From transient drift-diffusion dynamics, we show that the Purcell effect reduces the exciton density in the steady state and increases the photoluminescent yield, thereby reducing defect generation rates and extending the device lifetime. We control the radiative rate of excitons in microcavities, thereby connecting the exciton energy and decay rates with the observed device lifetime. The device lifetime is shown to follow a power-law dependence on the Purcell factor (PFm) with m=1.5 to 2.5, dependent on the TTA-to-TPA ratio and photoluminescence quantum yield. From our analysis, a fivefold increase in PF has the potential to extend the blue PHOLED lifetime by up to 2 orders of magnitude, making the blue PHOLED lifetime comparable to that of state-of-the-art green PHOLEDs. Published by the American Physical Society 2024

The Hidden Mechanism: Excited‐State Proton‐Electron Pair Transfer in Metal Nanocluster Emission

AbstractComprehending the underlying factors that govern photoluminescence (PL) in metal nanoclusters (NCs) under physiological conditions remains a highly intriguing and unresolved challenge, particularly for their biomedical applications. In this study, we evaluate the critical role of excited‐state proton‐coupled electron transfer in the emission of metal NCs. Our findings demonstrate that hydronium ion (H3O+) binding can trigger a nonlinear, pH‐dependent excited‐state concerted electron proton transfer (CEPT) reaction. This involves simultaneous electron transfer from the Au(0) core to the Au(I)−ATT (ATT denotes 6‐aza‐2‐thiothymidine) surface and proton transfer from H3O+ to the ATT ligand in a single step, greatly promoting vibrations and rotations of the Au(I)−ATT surface, resulting in substantial PL quenching of Au10(ATT)6 NCs. Further analyses show that the unique CEPT dynamics are strongly influenced by the opposing effects of increased reorganization energy and a larger pre‐exponential factor on the electron transfer rate. Moreover, the proposed excited‐state CEPT process is found to be prevalent in core–shell relaxation metal NCs, such as Au25(SR)18 (SR denotes thiolate) NCs, and serves as an important factor in limiting their PL emission. By simply controlling the pKa of the ligands, the emission performance of Au25(SR)18 can be easily regulated in physiological environments.

A butterfly-shaped acceptor with rigid skeleton and unique assembly enables both efficient organic photovoltaics and high-speed organic photodetectors.

It remains challenging to design efficient bifunctional semiconductor materials in organic photovoltaic and photodetector devices. Here, we report a butterfly-shaped molecule, named WD-6, which exhibits low energy disorder and small reorganization energy due to its enhanced molecular rigidity and unique assembly with strong intermolecular interaction. The binary photovoltaic device based on PM6:WD-6 achieved an efficiency of 18.41%. Notably, an efficiency of 19.42% was achieved for the ternary device based on PM6:BTP-eC9:WD-6. Moreover, the photodetection device based on WD-6 demonstrated an ultrafast response speed (205ns response time at λ of 820nm) and a high cutoff frequency of -3dB (2.45MHz), surpassing the values of most commercial Si photodiodes. Based on these findings, we showcased an application of the WD-6-based photodetection device in high-speed optical communication. These results offer valuable insights into the design of organic semiconductor materials capable of simultaneously exhibiting high photovoltaic and photodetective performance.

Role of cavity strong coupling on single electron transfer reaction rate at electrode-electrolyte interface.

The physicochemical properties of molecules can be modulated through polariton formation under strong electromagnetic confinement. Here, we discuss the possibility of exploiting this phenomenon to increase the electron transfer rate at an electrode-electrolyte interface. Electron transfer theory under strong electromagnetic confinement can be extended to the electrode-electrolyte interface, and single-electron transfer reactions can be simulated using Gerischer's theory. Although single electron transfer in free space is well described using Marcus theory, the vacuum electric field can facilitate an additional electron transfer pathway via virtual photon excitation under cavity strong coupling conditions. Therefore, this binary reaction pathway for single electron transfer can yield a quasi-two-particle electron transfer process. This quantum behavior can dominate when the mode volume is small and when there are a large number of molecules in the vacuum electric field. Exploitation of polaritons in single electron transfer reactions can lead to enhanced electrochemical energy conversion systems.

Machine learning assisted designing of hole-transporting materials for high performance perovskite solar cells

In recent years, the advancement of perovskite solar cells has accelerated, leading to continuous performance improvements. Over the past few years, machine learning (ML) has gained popularity among scientists researching perovskite solar cells. In this study, ML is used to screen hole-transporting materials for perovskite solar cells. To construct machine-learning (ML) models, data from prior investigations are collected. Out of four machine learning algorithms trained for predicting reorganization energy (Rh), the gradient boosting regression model stood out as the most effective, attaining an R2 value of 0.89. Data visualization analysis is then utilized to scrutinize the patterns within the dataset. 10,000 new compounds are generated. Chemical space of generated compounds is visualized using various measures. Minor structural modifications resulted in only a slight alteration in reorganization energy (Rh). The newly introduced multidimensional framework has the potential to efficiently screen materials in a short amount of time.

Structural, Solvent, and Temperature Effects on Protein Junction Conductance.

Cytochrome b562 is a small redox-active heme protein that has served as an important model system for understanding biological electron transfer processes. Here, we present a comprehensive theoretical study of electron transport mechanisms in protein-metal junctions incorporating cytochrome b562 using a multi-scale computational approach. Employing molecular dynamics (MD) simulations, we generated junction geometries for both vacuum-dried and solvated conditions, with the protein covalently bound to gold contacts in various configurations. Coherent tunneling, described by the Landauer-Buttiker formalism within the density functional theory (DFT) framework, is compared to the incoherent hopping charge transport mechanism captured by the semi-classical Marcus theory. The tunneling was identified as the dominant mechanism explaining the experimental data measured on the cytochrome b562 junctions, exhibiting exponential yet very shallow distance dependence. While the structural orientations and protein contacts with the electrodes influence the junction conductance significantly, the solvation effects are relatively small, affecting the electronic properties mostly via the adsorption arrangement. On the other hand, the considerable temperature dependence of the conductance was found strong only for hopping, while the tunneling current magnitudes remain practically unaffected and are a good indicator of the coherent mechanism in this case.

Microscopic Origin of Twist-Dependent Electron Transfer Rate in Bilayer Graphene.

Using molecular simulation and continuum dielectric theory, we consider how electrochemical kinetics are modulated by the twist angle in bilayer graphene electrodes. By establishing a connection between the twist angle and the screening length of charge carriers within the electrode, we investigate how tunable metallicity modifies the statistics of the electron transfer energy gap. Constant potential molecular simulations show that the activation free energy for electron transfer increases with screening length, leading to a non-monotonic dependence on the twist angle. The twist angle alters the density of states, tuning the number of thermally accessible channels for electron transfer and the reorganization energy by affecting the stability of the vertically excited state through attenuated image charge interactions. Understanding these effects allows us to express the Marcus rate of interfacial electron transfer as a function of the twist angle in a manner consistent with experimental observations.

Development of cost-effective diphenylamine substituted hole transporting materials for organic and perovskite solar cells

In recent years, material developments have continued to increase the performances of organic and perovskite solar cells (PSCs). Therefore, herein, we designed (HRN1-HRN11) and characterized eleven new hole transport materials (HTM) for PSCs. A systematic investigation has been conducted to investigate the optoelectrical characteristics of these HTMs. The optical characteristics and structure of these modeled HTMs have been analyzed using density functional theory (DFT) and time-dependent (TD-DFT). Ionization potential, electron density difference (EDD), electron and hole reorganizational energies, charge transfer analysis, transition density matrix, and molecular electrostatic potential analysis were performed to investigate the potential of these designed series (HRN1-HRN11) for PSCs. In comparison to the synthetic reference molecule (HRN), which has a band gap of 3.64 eV and a wavelength of 388.69 nm, the newly developed compounds (HRN1-HRN11) show promising optoelectronic qualities with much lower energy gaps (up to 2.01 eV) and absorbed maximum absorption wavelength (940.99 nm). Together with their excellent hole and electron transport capabilities, improved open-circuit voltage values of 1.06–1.34 eV are calculated. The acceptor and donor regions of HRN2, HRN7, and HRN1 exhibit great charge mobility and have the lowest electron reorganization energy. HRN9 has the greatest reorganization energy of hole (λh) value among all designed molecules. The work emphasizes designing suitable photovoltaic materials to produce highly efficient solar cell devices.

Ultrasound-Assisted Remote Benzylic C(sp3)-H Alkylation of N-Fluoroamides with Enol Silanes.

We have developed an ultrasound-assisted remote benzylic C(sp3)-H alkylation of N-fluorobenzamides with enol silanes; a series of β-aryl substituted propiophenones was generated in good to high yields. This reaction represents a formal C(sp3)-C(sp3) coupling and features simplicity, high efficiency, and wide substrate scope in a multiple-step sequential process, which involves N-F homolysis, 1,5-hydrogen atom transfer, benzylic radical addition, oxidation by copper(II) salt, and removal of the trimethylsilyl group. Also, DFT theoretical calculations and Marcus theory were employed to consolidate the proposed reaction mechanism.

Multiple Resonance Quasi-fluorescence from BN-Doped Aromatic Compounds Modified with "Naphthalene" Units Approaches the BT.2020 Green Light Standard.

Developing fluorophores that conform to the Broadcast Service Television 2020 (BT.2020) standard presents a formidable challenge. Here, we propose an innovative approach that integrates two and three-boron/nitrogen (BN2)-embedded [4]helicene subunits with naphthalene, resulting in the synthesis of two novel narrowband bright green quasi-fluorescent emitters, NT-2B and NT-3B for ultra-high-definition displays. These emitters exhibit minimal reorganization energy and Huang-Rhys factor, emitting at 510 and 511 nm in dilute toluene solution with exceptionally narrow full width at half maximum values of 15 and 14 nm, respectively. Notably, NT-2B demonstrates an impressive photoluminescence quantum yield of 92.5 %, rapid radiative decay rate, and slow non-radiative decay rate. Owing to their narrowband emission characteristics and outstanding optoelectronic properties, corresponding OLEDs based on NT-2B demonstrate a high external quantum efficiency of 30.6 %, with an FWHM value of 21.5 nm and a CIEy of 0.74, positioning it as one of the leading narrow-band green emitters.

Multiple Resonance Quasi‐fluorescence from BN‐Doped Aromatic Compounds Modified with “Naphthalene” Units Approaches the BT.2020 Green Light Standard

AbstractDeveloping fluorophores that conform to the Broadcast Service Television 2020 (BT.2020) standard presents a formidable challenge. Here, we propose an innovative approach that integrates two and three‐boron/nitrogen (BN2)‐embedded [4]helicene subunits with naphthalene, resulting in the synthesis of two novel narrowband bright green quasi‐fluorescent emitters, NT‐2B and NT‐3B for ultra‐high‐definition displays. These emitters exhibit minimal reorganization energy and Huang–Rhys factor, emitting at 510 and 511 nm in dilute toluene solution with exceptionally narrow full width at half maximum values of 15 and 14 nm, respectively. Notably, NT‐2B demonstrates an impressive photoluminescence quantum yield of 92.5 %, rapid radiative decay rate, and slow non‐radiative decay rate. Owing to their narrowband emission characteristics and outstanding optoelectronic properties, corresponding OLEDs based on NT‐2B demonstrate a high external quantum efficiency of 30.6 %, with an FWHM value of 21.5 nm and a CIEy of 0.74, positioning it as one of the leading narrow‐band green emitters.

Improving Optoelectronic Properties of Acceptor–Donor–Acceptor‐Type Non‐Fullerene Acceptors Containing Extended Fused Ring Donor Units for Efficient Organic Semiconductors

Developing efficient small molecule‐based non‐fullerene acceptors (NFAs) has gained huge attention in fabricating high‐efficiency and stable organic solar cells (OSCs). Herein, we designed and characterized eight new NFAs for OSCs. To investigate the potential of these newly designed NFAs series (IBH1–IBH8) for OSCs, various advanced quantum chemical simulation approaches are used and compared with the synthetic reference molecule IBH–R. Due to the extended donor cores, the IBH1–IBH8 molecules possess strong intramolecular and intermolecular interactions, which helps improve the thin‐film surface crystallinity. Moreover, the designed IBH1–IBH8 molecules present improved UV–visible absorption, narrower bandgaps, lower excitation, and binding energies, and improved photovoltaic characteristics. Furthermore, the impact on the intrinsic properties such as transition density matrix, density of state, electrostatic potential, distribution of frontier molecular orbitals, and reorganizational energies of holes and electrons are estimated. Additionally, the charge‐transfer phenomenon by establishing a donor:acceptor blend (PTB7–Th:IBH4) is analyzed, their geometric analyses are studied, and a good charge‐shifting process is found at the donor:acceptor interface. With these results, we demonstrated the enhancements in the optoelectronic and photovoltaic characteristics of OSCs by performing a simple end‐capped modulation. Hence, these molecules are recommended for the development of efficient and cost‐effective OSCs.

The Buddleja globosa (Matico) as natural Dye Sensitized Solar Cell: An experimental and theoretical studies based in TD-DFT/ periodic-DFT

The dye sensitizers coming from Buddleja Globosa, a Chilean regional flora, were analyzed and evaluated as a natural dye for the assembly of DSSC. The behavior toward the photoexcitation and electron injection steps was analyzed using time dependent functional theory (TD-DFT) and periodic (Periodic-DFT) calculations using a dye@(TiO2)48 model. The molecules analyzed present in the leaves were verbascoside, luteolin 7-O-glucoside, apigenin 7-O-glucoside, luteolin and gallic acid. The photoexcitation is driven by a π−π* transition localized in the frontier orbitals. These exhibit a ΔEHOMO−LUMO of approximately 4.0 eV which is very broad to facilitate an efficient photoexcitation process even though the LUMO density is localized in the acceptors group. In the adsorption and electron injection was found that the gallic acid and verbascoside facilitate a greater electron transport toward the metallic surface than the other dyes (ΔGinj = -1.52 and -1.03 eV, respectively). This was explained due to a low electron and hole reorganization energy in the gallic acid and verbacoside, respectively. Therefore, the greatest electron injection is originated due to a fast electron-hole transfer. Experimentally, a low overall conversion efficiency (η) was found. Thus, based in the computational discussion, this low efficiency is governed by the behaviour of the photoexcitation and not by the electron injection response.

Electrolyte Effects in Electrocatalytic Kinetics†

Comprehensive SummaryTuning electrolyte properties is a widely recognized strategy to enhance activity and selectivity in electrocatalysis, drawing increasing attention in this domain. Despite extensive experimental and theoretical studies, debates persist about how various electrolyte components influence electrocatalytic reactions. We offer a concise review focusing on current discussions, especially the contentious roles of cations. This article further examines how different factors affect the interfacial solvent structure, particularly the hydrogen‐bonding network, and delves into the microscopic kinetics of electron and proton‐coupled electron transfer. We also discuss the overarching influence of solvents from a kinetic modeling perspective, aiming to develop a robust correlation between electrolyte structure and reactivity. Lastly, we summarize ongoing research challenges and suggest potential directions for future studies on electrolyte effects in electrocatalysis. Key ScientistsIn 1956, Marcus theory was developed to describe the mechanism of outer‐sphere electron transfer (OS‐ET). In 1992, Nocera et al. directly measured proton‐coupled electron transfer (PCET) kinetics for the first time, and their subsequent research in 1995 investigated the effects of proton motion on electron transfer (ET) kinetics. In 1999 and 2000, Hammes‐schiffer et al. developed the multistate continuum theory for multiple charge reactions and deduced the rate expressions for nonadiabatic PCET reactions in solution, laying the theoretical foundation for the analysis of PCET kinetics in electrochemical processes. In 2006, Saveant et al. verified the concerted proton and electron transfer (CPET) mechanism in the oxidation of phenols coupled with intramolecular amine‐driven proton transfer (PT). Their subsequent work in 2008 reported the pH‐dependent pathways of electrochemical oxidation of phenols.Electrolyte effects in electrocatalysis have gained emphasis in recent years. In 2009, Markovic's pioneering work proposed non‐covalent interactions between hydrated alkaline cations and adsorbed OH species in oxygen reduction reaction (ORR)/hydrogen oxidation reaction (HOR). In 2011, Markovic et al. significantly enhanced hydrogen evolution reaction (HER) activity in alkaline solution by improving water dissociation, which was assumed to dominate the sluggish HER kinetics in such media. In comparation, Yan et al. applied hydrogen binding energy (HBE) theory in 2015 to explain the pH‐dependent HER/HOR activity. Cations play a significant role in regulating the selectivity and activity of carbon dioxide reduction (CO2RR). In 2016 and 2017, Karen Chan et al. introduced the electric field generated by solvated cations to explain the cation effects on electrochemical CO2RR. Conversely, in 2021, Koper et al. suggested that short‐range electrostatic interactions between partially desolvated metal cations and CO2 stabilized CO2 and promoted CO2RR.Recent researches have combined the exploration of the electrical double layer (EDL) structure with theoretical analysis of PCET kinetics. In 2019, Huang et al. developed a microscopic Hamiltonian model to quantitatively understand the sluggish hydrogen electrocatalysis in alkaline media. In 2021, two meticulous studies from Shao‐Horn's group analyzed the effects of cations on reorganization energy and the impacts of hydrogen bonds between proton donors and acceptors on proton tunneling kinetics, respectively. Electrolyte effects on proton transport process were researched in recent years. In 2022, Hu et al. and Chen et al. proposed that the cation‐induced electric field distribution and pH‐dependent hydrogen bonding network connectivity played essential roles in proton transport, separately.

The Hidden Mechanism: Excited-State Proton-Electron Pair Transfer in Metal Nanocluster Emission.

Comprehending the underlying factors that govern photoluminescence (PL) in metal nanoclusters (NCs) under physiological conditions remains a highly intriguing and unresolved challenge, particularly for their biomedical applications. In this study, we evaluate the critical role of excited-state proton-coupled electron transfer in the emission of metal NCs. Our findings demonstrate that hydronium ion (H3O+) binding can trigger a nonlinear, pH-dependent excited-state concerted electron proton transfer (CEPT) reaction. This involves simultaneous electron transfer from the Au(0) core to the Au(I)-ATT (ATT denotes 6-aza-2-thiothymidine) surface and proton transfer from H3O+ to the ATT ligand in a single step, greatly promoting vibrations and rotations of the Au(I)-ATT surface, resulting in substantial PL quenching of Au10(ATT)6 NCs. Further analyses show that the unique CEPT dynamics are strongly influenced by the opposing effects of increased reorganization energy and a larger pre-exponential factor on the electron transfer rate. Moreover, the proposed excited-state CEPT process is found to be prevalent in core-shell relaxation metal NCs, such as Au25(SR)18 (SR denotes thiolate) NCs, and serves as an important factor in limiting their PL emission. By simply controlling the pKa of the ligands, the emission performance of Au25(SR)18 can be easily regulated in physiological environments.