Redox Centers Research Articles

A Minireview of Multimetallic Iron‐Based Oxides for Supercapacitive Negative Electrode Materials

The serious mismatch between the positive and negative electrodes of supercapacitors (SCs) makes it imperative to develop high‐performance negative electrode materials. Among them, multimetallic iron‐based oxides (MIBOs) are intensively investigated attributed to their high theoretical specific capacitance, wide operating potential window, copious electrochemical active sites, variable metal oxidation states, and abundant redox centers. This paper briefly introduces some essential information on SCs and the most common synthesis methods of MIBOs. Also, the research progress of several important MIBOs and their composites is discussed. Finally, the existing problems and challenges of MIBOs are summarized and future outlooks are likewise proposed.

Crystal structure of the alternative complex III from the phototrophic bacterium Chloroflexus aurantiacus.

Alternative complex III (ACIII) is a multi-subunit quinol:electron acceptor oxidoreductase that couples quinol oxidation with transmembrane proton translocation in bacterial respiratory and photosynthetic electron transport chains. Four ACIII cryoelectron microscopy (cryo-EM) structures are known. However, the effects of cryo-EM versus X-ray crystallography structure determination on ACIII structure are unclear. Here, we report a 3.25Å crystal structure of photosynthetic ACIII from Chloroflexus aurantiacus (CaACIIIp), revealing eight subunits (ActA-G and I) with four iron-sulfur clusters and six c-type hemes, a menaquinol-binding site, and two proton translocation passages. Structural comparisons with the previously reported cryo-EM structures reveal slight local conformational changes in the solvent-exposed regions of ActB, ActD, ActG, and the transmembrane (TM) helix of subunit I. The regions conferring structural flexibility possess low sequence conservation across species. However, the core functional modules containing the menaquinol-binding pocket, redox centers, and proton translocation passages remain unchanged, preserving the enzyme's activity.

Ultrafast Lattice Engineering for High Energy Density and High-Rate Sodium-Ion Layered Oxide Cathodes

Sodium-ion batteries attract significant interest for large-scale energy storage owing to abundant sodium reserves, while challenges remain in the high synthesis energy consumption, long synthesis period, and poor electrochemical performance of sodium-ion layered oxide materials. This study presents a general high-temperature thermal shock (HTS) strategy to synthesize and optimize sodium-ion layered oxides. The rapid ramping, sintering, and cooling processes minimize volatile sodium loss during HTS, facilitating the improvement of phase purity and effectively optimizing the microstructure of materials in a non-equilibrium state. As a proof of concept, Mn-based Na0.67MnO2 treated with HTS (NMO-HTS) suppresses Mn ion vacancy within transition material layers, thereby increasing the redox centers and lowering the Mn 3d orbital energy level. Besides, the formation of transition metal layer stacking faults mitigates the structural transformation and Na+-vacancies ordering arrangement during cycling. Consequently, the energy density of the NMO-HTS increases by 21.5% to 559 Wh kg-1, with an outstanding rate capability of 108 mAh g-1 at 10C and an impressive capacity retention of 93.7% after 300 cycles at 1C. In addition, we demonstrate the universality of HTS in synthesizing various other sodium-ion layered oxides, including nickel-based and iron-based cathodes, as well as in activating degraded materials.

Tethered heme domains in a triheme cytochrome allow for increased electron transport distances.

Decades of research describe myriad redox enzymes that contain cofactors arranged in tightly packed chains facilitating rapid and controlled intra-protein electron transfer. Many such enzymes participate in extracellular electron transfer (EET), a process which allows microorganisms to conserve energy in anoxic environments by exploiting mineral oxides and other extracellular substrates as terminal electron acceptors. In this work, we describe the properties of the triheme cytochrome PgcA from Geobacter sulfurreducens. PgcA has been shown to play an important role in EET but is unusual in containing three CXXCH heme binding motifs that are separated by repeated (PT)x motifs, suggested to enhance binding to mineral surfaces. Using a combination of structural, electrochemical, and biophysical techniques, we experimentally demonstrate that PgcA adopts numerous conformations stretching as far as 180 Å between the ends of domains I and III, without a tightly packed cofactor chain. Furthermore, we demonstrate a distinct role for its domain III as a mineral reductase that is recharged by domains I and II. These findings show PgcA to be the first of a new class of electron transfer proteins, with redox centers separated by some nanometers but tethered together by flexible linkers, facilitating electron transfer through a tethered diffusion mechanism rather than a fixed, closely packed electron transfer chain.

Close‐packed One‐dimensional Coordination Polymer Cathode with Fast Kinetics for Sodium‐ion Batteries

Sustainable sodium‐ion batteries (SIBs) have gained tremendous attention; however, the large‐sized Na+ poses serious challenges on the development of inorganic‐based cathodes. To overcome the issues, metal–organic electrode materials are appealing because they combine attractive characteristics of organic redox centers (e.g., flexibility, highly reversible redox properties, fast kinetics (regardless of size and charge of guest ions), structural/redox tunability, and resource abundance) with structural stability arising from metal‐ligand coordination. Herein, a one‐dimensional copper‒benzoquinoid coordination polymer (CP), [CuL(Py)2]n, (LH4 = 1,4‐dicyano‐2,3,5,6‐tetrahydroxybenzene, Py = pyridine) is investigated as cathode for SIBs. As opposed to most CPs reported for SIBs which possess high porosity and surface area, this close‐packed CP can deliver discharge capacity as high as 277 mAh g‒1 at 2C (~523 mA g‒1), and at extremely high rates of 50C and 300C (~13 and 78 A g‒1), reversible capacities of 131 and 74 mAh g‒1 still can be delivered, respectively. The transport kinetics of Na+ in [CuL(Py)2]n is found to be even faster than that of Li+ despite the close‐packed structure. The mechanistic and kinetic studies have been performed. The findings gained in this work undoubtedly unravel a potential design strategy for high‐performance metal–organic electrode materials for emerging post‐Li‐ion batteries.

The Switching of the Type of a ROS Signal from Mitochondria: The Role of Respiratory Substrates and Permeability Transition

Flashes of superoxide anion (O2−) in mitochondria are generated spontaneously or during the opening of the permeability transition pore (mPTP) and a sudden change in the metabolic state of a cell. Under certain conditions, O2− can leave the mitochondrial matrix and perform signaling functions beyond mitochondria. In this work, we studied the kinetics of the release of O2− and H2O2 from isolated mitochondria upon mPTP opening and the modulation of the metabolic state of mitochondria by the substrates of respiration and oxidative phosphorylation. It was found that mPTP opening leads to suppression of H2O2 emission and activation of the O2− burst. When the induction of mPTP was blocked by its antagonists (cyclosporine A, ruthenium red, EGTA), the level of substrates of respiration and oxidative phosphorylation and the selective inhibitors of complexes I and V determined the type of reactive oxygen species (ROS) emitted by mitochondria. It was concluded that upon complete and partial reduction and complete oxidation of redox centers of the respiratory chain, mitochondria emit H2O2, O2−, and nothing, respectively. The results indicate that the mPTP- and substrate-dependent switching of the type of ROS leaving mitochondria may be the basis for O2−- and H2O2-selective redox signaling in a cell.

Zero-Strain Sodium Nickel Ferrocyanide as Cathode Material for Sodium-Ion Batteries with Ultra-Long Lifespan.

Prussian blue analogues are recognized as one of the most promising cathode materials for sodium-ion batteries (SIBs) owing to the open 3D framework structure with large interstitial sites and developed Na-ion diffusion channels. However, high content of anion vacancy and poor structural stability have hampered the prospect of their application. In this work, sodium nickel ferrocyanide (Na1.34Ni[Fe(CN)6]0.92, NNHCF) is proposed as cathode material for SIBs. N-coordinated Ni-ion can boost NNHCF to possess less Fe[(CN)6]4- defect, low Na-ion migration barrier, and more negative formation energy compared with Na0.91Cu[Fe(CN)6]0.77 (NCHCF), thus exhibiting more active sites, fast electrochemical kinetics behavior and great structure stability. It is confirmed that NNHCF undergoes a solid solution mechanism without phase evolution for reversible Na-ion intercalation/deintercalation, employing Fe associated with C atom as redox center for charge compensation. Therefore, NNHCF contributes a high initial energy density of 180.94 Wh·g-1 at 10 mA·g-1, excellent rate capability, superior cycling stability with ultra-long lifespan of 13000 cycles, and low fading rate of 0.0027% per cycle at 500 mA·g-1. This work sheds light on the construction of low-defect PBA cathodes with outstanding dynamics and stability.

Highly Conductive Two-Dimensional FeTHBQ/Graphene Nanocomposite as the Cathode Material for Lithium-Ion Batteries.

Constructing high-performance coordination polymer (CP) cathodes for lithium-ion batteries based on the redox reactions of both high-potential transition metal ions and high-capacity organic ligands has attracted extensive attention. However, CP cathodes suffer from structural degradation, low electrical conductivity, and sluggish diffusion kinetics, resulting in poor cycling stability and inferior rate capability. Herein, the ultrafine FeTHBQ (THBQ = tetrahydroxy-1,4-benzoquinone) CP nanoparticles in situ grew on both sides of graphene nanosheets to form the uniform two-dimensional (2D) FeTHBQ/Graphene nanocomposite with a sandwich structure via a one-pot solvothermal method. The highly conductive graphene skeleton promotes the electronic conduction and structural stability for the 2D FeTHBQ/Graphene nanocomposite. Besides, compared with bulk FeTHBQ, the primary FeTHBQ nanoparticles in the FeTHBQ/Graphene nanocomposite have smaller particle sizes with larger specific surface areas. This not only shortens the Li+ diffusion distance in the FeTHBQ crystal but also benefits Li+ transfer between the electrolyte and the electrode. In the FeTHBQ/Graphene nanocomposite, the active material of FeTHBQ manifested multiple redox centers of transition metal ions (Fe3+/Fe2+) and carbonyls (C═O/C-O-) in THBQ ligands. Owing to the enhancements of structural stability, electronic conduction, and Li+ diffusion kinetics, the 2D FeTHBQ/Graphene nanocomposite presented a high lithium-ion storage capacity of 217.2 mA h g-1 at 50 mA g-1, a fast rate capability of 79.1 mA h g-1 at 5000 mA g-1, and a stable cycling performance of 87.2 mA h g-1 at 500 mA g-1 after 100 cycles. This work sheds light on the great opportunity for optimizing the electrochemical performances of CP-based functional electrode materials by combining with conductive substrates.

Immobilization of Membrane-Associated Protein Complexes on SERS-Active Nanomaterials for Structural and Dynamic Characterization.

Exploring the structural basis of membrane proteins is significant for a deeper understanding of protein functions. In situ analysis of membrane proteins and their dynamics, however, still challenges conventional techniques. Here we report the first attempt to immobilize membrane protein complexes on surface-enhanced Raman scattering (SERS)-active supports, titanium dioxide-coated silver (Ag@TiO2) nanoparticles. Biocompatible immobilization of microsomal monooxygenase complexes is achieved through lipid fission and fusion. SERS activity of the Ag@TiO2 nanoparticles enables in situ monitoring of protein-protein electron transfer and enzyme catalysis in real time. Through SERS fingerprints of the monooxygenase redox centers, the correlations between these protein-ligand interactions and reactive oxygen species generation are revealed, providing novel insights into the molecular mechanisms underlying monooxygenase-mediated apoptotic regulation. This study offers a novel strategy to explore structure-function relationships of membrane protein complexes and has the potential to advance the development of novel reactive oxygen species-inducing drugs for cancer therapy.

S-scheme3D/3D Bi0/BiOBr/P Doped g-C3 N4 with Oxygen Vacancies (Ov) for Photodegradation of Pharmaceuticals: In-situ H2O2 Production and Plasmon Induced Stability.

Complications accompanying photocatalyst stability and recombination of exciton charges in pollutants degradation has been addressed through the construction of heterojunctions, especially S-scheme heterojunction with strong and distinctive redox centres. Herein, an S-scheme BiOBr (BOR) and g-C3N4PO4 (CNPO) catalyst (BORCNPO) with oxygen vacancy (Ov) was synthesized for levofloxacin (LVX) and oxytetracycline (OTC) photodegradation under visible light. The 3D/3D BORCNPO catalyst possessed C-O-Br bridging bonds for efficient charge transfer during the fabrication of S-scheme heterojunction. In-situ H2O2 formation affirmed by potassium titanium (IV) oxalate spectrophotometric method improved the mineralization ability of BORCNPO7.5 catalyst. Bi0 surface plasmon resonance (SPR) enhanced formation and involvement of ⋅O2 - and the stability of the catalyst which increased reaction rate with increasing cycling experiments. XPS and radical trapping experiments supported the S-scheme charge transfer mechanism formation with high degradation rate of LVX which was 3 times higher than OTC degradation rate. Mineralization of pollutants and their intermediates were demonstrated with florescence excitation and emission matrix (FEEM) and quadruple time of flight high performance liquid chromatography (QTOF-HPLC). This work advances development of highly stable and efficient catalysts for photodegradation of pollutants through the formation of S-scheme heterostructure.

NADPH Oxidases-Inspired Reactive Oxygen Biocatalysts with Electron-Rich Pt Sites to Potently Amplify Immune Checkpoint Blockade Therapy.

Clinical immune checkpoint blockade (ICB)-based immunotherapy of malignant tumors only elicits durable responses in a minority of patients, primarily due to the highly immunosuppressive tumor microenvironment. Although inducing immunogenic cell death (ICD) through reactive oxygen biocatalyst represents an attractive therapeutic strategy to amplify ICB, currently reported biocatalysts encounter insurmountable challenges in achieving high ROS-generating activity to induce potent ICD. Here, inspired by the natural catalytic characteristics of NADPH oxidases, the design of efficient, robust, and electron-rich Pt-based redox centers on the non-stoichiometric W18O49 substrates (Pt─WOx) to serve as bioinspired reactive oxygen biocatalysts to potently activate the ICD, which eventually enhance cancer immune responses and amplifies the ICB-based immunotherapy is reported. These studies demonstrate that the Pt─WOx exhibits rapid electron transfer capability and can promote the formation of electron-rich and low oxophilic Pt redox centers for superior reactive oxygen biocatalysis, which enables the Pt─WOx-based inducers to trigger endoplasmic reticulum stress directly and stimulate immune responses potently for amplifying the anti-PD-L1-based ICB therapy. This bioinspired design provides a straightforward strategy to engineer efficient, robust, and electron-rich reactive oxygen biocatalysts and also opens up a new avenue to create efficient ICD inducers for primary/metastatic tumor treatments.

Fully Integrated Biosensing System for Dynamic Monitoring of Sweat Glucose and Real-Time pH Adjustment Based on 3D Graphene MXene Aerogel.

The development of noninvasive glucose sensors capable of continuous monitoring without restricting user mobility is crucial, particularly for managing diabetes, which demands consistent and long-term observation. Traditional sensors often face challenges with accuracy and stability that curtail their practical applications. To address these issues, we have innovatively applied a three-dimensional porous aerogel composed of Ti3C2Tx MXene and reduced graphene oxide (MX-rGO) in electrochemical sensing. It significantly reduces the electron-transfer distance between the enzyme's redox center and the electrode surface while firmly anchoring the enzyme layer to effectively prevent any leakage. Another pivotal advancement in our study is the integration of the sensor with a real-time adaptive calibration mechanism tailored specifically for analyzing sweat glucose. This sensor not only measures glucose levels but also dynamically monitors and adjusts to pH fluctuations in sweat. Such capabilities ensure the precise delivery of physiological data during physical activities, providing strong support for personalized health management.

Synergistic impact of Fe–Zr in novel hybrid aminoclay catalytic TFC membrane for ultrafast emerging pollutant remediation

Finding new class of materials to overcome limitation in conventional membranes is a challenging task. Use of naturally stable and sustainable alternative materials stock is an emerging task. In this direction, a novel iron-zirconium hybrid aminoclay (FZ-AC) has emerged as a promising catalyst effectively employed to alleviate fouling concerns within the framework of a biopolymer-based thin film composite (TFC), constructed on a cellulose acetate (CA) support. Notably, FZ-AC exhibits remarkable catalytic activity in the degradation of foulants through potential free radicals generated from Fe and Zr active centres in synergy with oxidising agent. The optimised catalytic membrane (FZ-TFC-1) exhibited an ultrafast degradation of congo red (CR), eriochrome black-T (EBT), crystal violet (CV), methylene blue (MB), red-brown dye (RBn), bisphenol-A (BPA), azithromycin (AZC), and Cr(VI) within 4 min. The cooperative action of redox centres of Fe and Zr metal ions synergistically accelerated the swift production of reactive species and facilitated the efficient degradation of pollutants within a notably short timeframe. Furthermore, >95% of above dyes rejection was achieved with >67 L m−2.h−1 of flux. The results of a long-term study demonstrated that FZ-TFC membranes exhibit exceptional stability, retaining their performance for a duration up to 150 h. This extended period of stability underscores the superiority of these membranes over alternative counterparts, suggesting their robustness and reliability for sustained operation in various applications. This strategic utilization of FZ-AC representing a promising avenue for enhancing the efficacy and longevity of nanofiltration membranes, thereby advancing the frontier of membrane-based separation technologies.

Pillar-Supported 2D Layered MOFs with Abundant Active-Site Distributions for High-Performance Alkaline Supercapacitors.

The development of two-dimensional (2D) layered metal-organic frameworks (MOFs) through precise molecular-level design and synthesis has emerged as a prominent research endeavor. However, the utilization of MOFs in their pristine form as electrodes for supercapacitors poses a significant challenge due to their limited tolerance in alkaline environments. To address these issues, we have developed Co- and Cu-based pillar-layered MOFs by regulating the structure of their inner layers through introducing an alkaline N-containing "pillar" to enhance the performance of alkaline supercapacitor electrodes. From the microstructure study and theoretical calculation, the high-density redox centers and efficient chemical bonding modes of Co-MOF determine a unique electron conduction pathway, resulting in excellent energy storage performance. This study underscores the significance of chemical bonding modes and active-site distribution in enhancing the energy storage capabilities of pillar-layered MOFs in alkaline environments, presenting a promising approach for the development of high-performance MOF-based materials for supercapacitor applications.

Multifunctional Porous Organic Polymer Anode with Desired Redox Potential and Capacity for High-Performance Aqueous Sodium-Ion and Ammonium-Ion Batteries.

Aqueous sodium-ion batteries (ASIBs) and aqueous ammonium-ion batteries (AAIBs) attract great attention due to their low cost, safety, and environmental friendliness, but the lack of suitable electrodes with competitive capacity and redox potential limits their practical applications. Herein, we report a porous organic polymer (POP) with multiple redox processes as anodes for ASIBs and AAIBs. This POP displays desired redox potential and shows high reversible capacity of more than 200 mAh g-1 in both ASIBs and AAIBs. Full cells configured by this POP anode also display excellent performance (about 80% and 60% capacity retention over 1000 cycles in ASIBs and AAIBs). In addition, the intercalation chemistry of inorganic NH4+ with this POP is investigated, illustrating that the pyrazine sites in this POP are the redox centers to reversibly combine with NH4+. This work provides a promising and alternative anode for ASIBs and AAIBs and paves a new way for the development of novel organic materials for other aqueous battery systems.

Tuning Electron Transfer Coupling and Exchange Interaction in Bis-triarylamine Radical Cations and Dications by Bridge Electron Density.

The influence of the electron density of a bridge connecting two redox centers on both the intervalence hole transfer and the magnetic superexchange was investigated in a series of bridged bis-triarylamine mono- and dications. In this series, the bridge was 2,7-fluorenyl, where the bridge electron density was modified by substituents at the 9-position. For the mixed-valence monocations, the observation of both an intervalence charge transfer (IVCT) band and an absorption band associated with an electron transfer from the bridging fluorene to the triarylamine radical cation centers allowed determination of the electron transfer couplings in the framework of the three-state generalized Mulliken-Hush theory. Comparison of the derived couplings with those obtained from a classical two-state approach demonstrates an enhancement of the electronic coupling which increases with decreasing bridge state energy. For the dicationic diradical counterparts, the singlet-triplet gap (exchange interaction) was determined both experimentally and by quantum chemical methods. Hereby, an increase of antiferromagnetic coupling with a lowering of the bridge state energy by electron donating substituents was observed. Analysis of the involved molecular orbitals suggests that the ferromagnetic coupling is inversely proportional to the square of the bridge energy, which is also supported by the experimental findings. This influence of the bridge state energy on both types of interactions, electron transfer and magnetic exchange, provides a design guideline for fine-tuning the properties of electronically coupled organic redox dyads by variation of the bridge electron density.

Harnessing 4f Electron Itinerancy for Integrated Dual-Band Redox Systems Boosts Lithium-Oxygen Batteries Electrocatalysis.

In-depth comprehension and manipulation of band occupation at metal centers are crucial for facilitating effective adsorption and electron transfer in lithium-oxygen battery (LOB) reactions. Rare earth elements play a unique role in band hybridization due to their deep orbitals and strong localization of 4felectrons. Herein, we anchor single Ce atoms onto CoO, constructing a highly active and stable catalyst with d-fa dual-band redox center. It is discovered that the itinerant behavior of 4felectrons introduces an enhanced spin-orbit coupling effect, which facilitates ideal σ/π bonding and flexible adsorption between the Ce/Co active sites and *O. Simultaneously, the injection of localized Ce 4felectrons strengthens the orbital bonding capacity of Co-O, effectively inhibits the dissolution of Co sites and improves the structural stability of the cathode material. Bracingly, the Ce1/CoO-based LOB exhibits an ultra-low charge-discharge polarization (0.46 V) and stable cyclic performance (1088 hours). This work breaks through the traditional limitations in catalyst activity and stability, providing new strategies and theoretical insights for developing high-performance LOBs powered by rare-earth elements.

Dual redox centers in MnCo2O4 nanorod cathode for highly efficient capacitive deionization

Capacitive deionization (CDI) technology via faradic electrodes with active redox pairs has achieved tremendous success in desalination. However, the inner collaborative mechanisms of multi-redox centers in electrodes are rarely deep-analyzed. Thus, this work intensively investigated the inner enhanced mechanisms of multi-redox centers, starting from the dual-redox-based MnCo2O4 nanorod (MCO-NR) cathode in capacitive desalination. The electrochemical tests indicated a surface capacitive ratio of MCO-NR as high as 86 % when the scan rate was 100 mV s−1. Multi-dimensional CDI tests demonstrated that the highest capacity of MCO-NR could reach 61.78 mg g−1, with four theory models elaborating the electrosorption kinetics and maximum desalination capability. The refined ex-situ XPS measurements, carefully designed comparative experiments, and DFT calculations were used to analyze the Na+ (de)intercalation characteristics, the inner enhanced electrosorption mechanisms of dual redox centers, and the effects that the Mn redox center exerts on the MnCo2O4 structure. These results showed the superiority of dual- or multi-redox-center-based faradic capacitive desalination, providing a new perspective for designing high-property faradic electrode materials.

The interface electric field accelerated charge transfer kinetics of 1D/0D TiO2/Bi2Sn2O7 Z-scheme heterojunction with close contact interface significantly improves photothermal catalytic N2 reduction

The slow kinetics of charge transfer and weak redox ability hindered the practical application of photocatalytic N2 reduction. Therefore, in this article, Bi2Sn2O7 nanoparticles were grown in situ on the surface of TiO2 nanorods using a solvothermal method to form a 1D/0D TiO2/Bi2Sn2O7 (TBSO-15) Z-scheme heterojunction with a tight contact interface. The results of density functional theory calculations (DFT) and Kelvin probe force microscopy (KPFM) indicated that the difference in Fermi levels led to spontaneous rearrangement of charges at the heterojunction interface and the formation of a strong interfacial electric field (IEF). IEF provided a powerful driving force for the spatial separation of photogenerated charges, accelerating charge transfer dynamics. Secondly, the Z-scheme migration pathway of photo-generated charges between TiO2 and Bi2Sn2O7 enhanced the redox ability of TBSO-15 and formed a spatially separated redox center. In addition, molecular dynamics simulations (MD) showed that the photothermal effect significantly promoted the dynamic diffusion of N2 and H2O, accelerating the chemical reaction kinetics. Therefore, the synergistic effect of the two significantly improved the performance of Photothermal catalytic N2 reduction (PTC-NRR). After simulating solar irradiation for 2 h, the PTC-NRR performance of TBSO-15 achieved 327.25 μmoL·g−1 in pure water, which was 19.7 times that of TiO2 and 4.2 times that of Bi2Sn2O7, respectively. This study provides a reference for the synergistic effect of charge space transfer dynamics and photothermal effect to promote PTC-NRR.

Double Spin with a Twist: Synthesis and Characterization of a Neutral Mixed-Valence Organic Stable Diradical.

A convenient design strategy opens access to neutral open-shell mixed-valence species via the redox transformation of charged stable precursors, i.e., the spiro-fused borate anions. We have implemented this strategy for the synthesis of the first neutral mixed-valence diradical: two neutral mixed-valence radical fragments were assembled via a twisted biphenyl bridge. The diradical is a crystalline solid obtained in almost quantitative yield by using a facile synthetic procedure. It is stable at room temperature in the triplet ground state with a very small singlet/triplet gap. This metal-free diradical can reversibly form five redox states. The diradical exhibits an intense IVCT band in the NIR region and can be assigned as a Class 2 Robin-Day MV (mixed valence) system with weakly interacting redox centers. Computations suggest that this diradical finds itself in a unique tug-of-war between two electron delocalization patterns, Kekulé and non-Kekulé, which gives rise to two geometric isomers that are close in energy but drastically different in spin distribution and polarity. Such bistable spin-systems should be intrinsically switchable and promising for the design of functional spin devices. The scope and limitations of the new redox-strategy for the neutral MV radicals were also tested on other types of spiro-fused borates, revealing structural factors responsible for the evolution from transient to persistent and then to stable radicals.