Design Principles of Quinone Redox Systems for Advanced Sulfide Solid-State Organic Lithium Metal Batteries.

The emergence of solid-state battery technology presents a potential solution to the dissolution challenges of high-capacity small molecule quinone redox systems. Nonetheless, the successful integration of argyrodite-type Li6PS5Cl, the most promising solid-state electrolyte system, and quinone redox systems remains elusive due to their inherent reactivity. Here, a library of quinone derivatives is selected as model electrode materials to ascertain the critical descriptors governing the (electro)chemical compatibility and subsequently the performances of Li6PS5Cl-based solid-state organic lithium metal batteries (LMBs). Compatibility is attained if the lowest unoccupied molecular orbital level of the quinone derivative is sufficiently higher than the highest occupied molecular orbital level of Li6PS5Cl. The energy difference is demonstrated to be critical in ensuring chemical compatibility during composite electrode preparation and enable high-efficiency operation of solid-state organic LMBs. Considering these findings, a general principle is proposed for the selection of quinone derivatives to be integrated with Li6PS5Cl, and two solid-state organic LMBs, based on 2,5-diamino-1,4-benzoquinone and 2,3,5,6-tetraamino-1,4-benzoquinone, are successfully developed and tested for the first time. Validating critical factors for the design of organic battery electrode materials is expected to pave the way for advancing the development of high-efficiency and long cycle life solid-state organic batteries based on sulfides electrolytes.

Towards the 4 V-class n-type organic lithium-ion positive electrode materials: the case of conjugated triflimides and cyanamides.

Organic electrode materials have garnered a great deal of interest owing to their sustainability, cost-efficiency, and design flexibility metrics. Despite numerous endeavors to fine-tune their redox potential, the pool of organic positive electrode materials with a redox potential above 3 V versus Li+/Li0, and maintaining air stability in the Li-reservoir configuration remains limited. This study expands the chemical landscape of organic Li-ion positive electrode chemistries towards the 4 V-class through molecular design based on electron density depletion within the redox center via the mesomeric effect of electron-withdrawing groups (EWGs). This results in the development of novel families of conjugated triflimides and cyanamides as high-voltage electrode materials for organic lithium-ion batteries. These are found to exhibit ambient air stability and demonstrate reversible electrochemistry with redox potentials spanning the range of 3.1 V to 3.8 V (versus Li+/Li0), marking the highest reported values so far within the realm of n-type organic chemistries. Through comprehensive structural analysis and extensive electrochemical studies, we elucidate the relationship between the molecular structure and the ability to fine-tune the redox potential. These findings offer promising opportunities to customize the redox properties of organic electrodes, bridging the gap with their inorganic counterparts for application in sustainable and eco-friendly electrochemical energy storage devices.

Controlling Charge Transport in 2D Conductive MOFs─The Role of Nitrogen-Rich Ligands and Chemical Functionality.

Two-dimensional electrically conducting metal-organic frameworks (2D-e-MOFs) have emerged as a class of highly promising functional materials for a wide range of applications. However, despite the significant recent advances in 2D-e-MOFs, developing systems that can be postsynthetically chemically functionalized, while also allowing fine-tuning of the transport properties, remains challenging. Herein, we report two isostructural 2D-e-MOFs: Ni3(HITAT)2 and Ni3(HITBim)2 based on two new 3-fold symmetric ligands: 2,3,7,8,12,13-hexaaminotriazatruxene (HATAT) and 2,3,8,9,14,15-hexaaminotribenzimidazole (HATBim), respectively, with reactive sites for postfunctionalization. Ni3(HITAT)2 and Ni3(HITBim)2 exhibit temperature-activated charge transport, with bulk conductivity values of 44 and 0.5 mS cm-1, respectively. Density functional theory analysis attributes the difference to disparities in the electron density distribution within the parent ligands: nitrogen-rich HATBim exhibits localized electron density and a notably lower lowest unoccupied molecular orbital (LUMO) energy relative to HATAT. Precise amounts of methanesulfonyl groups are covalently bonded to the N-H indole moiety within the Ni3(HITAT)2 framework, modulating the electrical conductivity by a factor of ∼20. These results provide a blueprint for the design of porous functional materials with tunable chemical functionality and electrical response.

Bimetallic Anionic Organic Frameworks with Solid-State Cation Conduction for Charge Storage Applications.

A new phosphonate-based anionic bimetallic organic framework, with the general formula of A4 -Zn-DOBDP (wherein A is Li+ or Na+ , and DOBDP6- is the 2,5-dioxido-1,4-benzenediphosphate ligand) is prepared and characterized for energy storage applications. With four alkali cations per formula unit, the A4 -Zn-DOBDP MOF is found to be the first example of non-solvated cation conducting MOF with measured conductivities of 5.4×10-8  S cm-1 and 3.4×10-8  S cm-1 for Li4 - and Na4 - phases, indicating phase and composition effects of Li+ and Na+ shuttling through the channels. Three orders of magnitude increase in ionic conductivity is further attained upon solvation with propylene carbonate, placing this system among the best MOF ionic conductors at room temperature. As positive electrode material, Li4 -Zn-DOBDP delivers a specific capacity of 140 mAh g-1 at a high average discharge potential of 3.2 V (vs. Li+ /Li) with 90 % of capacity retention over 100 cycles. The significance of this research extends from the development of a new family of electroactive phosphonate-based MOFs with inherent ionic conductivity and reversible cation storage, to providing elementary insights into the development of highly sought yet still evasive MOFs with mixed-ion and electron conduction for energy storage applications.

Confining charge-transfer complex in a metal-organic framework for photocatalytic CO2 reduction in water.

In the quest for renewable fuel production, the selective conversion of CO2 to CH4 under visible light in water is a leading-edge challenge considering the involvement of kinetically sluggish multiple elementary steps. Herein, 1-pyrenebutyric acid is post-synthetically grafted in a defect-engineered Zr-based metal organic framework by replacing exchangeable formate. Then, methyl viologen is incorporated in the confined space of post-modified MOF to achieve donor-acceptor complex, which acts as an antenna to harvest visible light, and regulates electron transfer to the catalytic center (Zr-oxo cluster) to enable visible-light-driven CO2 reduction reaction. The proximal presence of the charge transfer complex enhances charge transfer kinetics as realized from transient absorption spectroscopy, and the facile electron transfer helps to produce CH4 from CO2. The reported material produces 7.3 mmol g-1 of CH4 under light irradiation in aqueous medium using sacrificial agents. Mechanistic information gleans from electron paramagnetic resonance, in situ diffuse reflectance FT-IR and density functional theory calculation.

Revealing the reversible solid-state electrochemistry of lithium-containing conjugated oximates for organic batteries.

In the rising advent of organic Li-ion positive electrode materials with increased energy content, chemistries with high redox potential and intrinsic oxidation stability remain a challenge. Here, we report the solid-phase reversible electrochemistry of the oximate organic redox functionality. The disclosed oximate chemistries, including cyclic, acyclic, aliphatic, and tetra-functional stereotypes, uncover the complex interplay between the molecular structure and the electroactivity. Among the exotic features, the most appealing one is the reversible electrochemical polymerization accompanying the charge storage process in solid phase, through intermolecular azodioxy bond coupling. The best-performing oximate delivers a high reversible capacity of 350 mAh g-1 at an average potential of 3.0 versus Li+/Li0, attaining 1 kWh kg-1 specific energy content at the material level metric. This work ascertains a strong link between electrochemistry, organic chemistry, and battery science by emphasizing on how different phases, mechanisms, and performances can be accessed using a single chemical functionality.

Tailoring a robust Al-MOF for trapping C2H6 and C2H2 towards efficient C2H4 purification from quaternary mixtures.

Light hydrocarbon separation is considered one of the most industrially challenging and desired chemical separation processes and is highly essential in polymer and chemical industries. Among them, separating ethylene (C2H4) from C2 hydrocarbon mixtures such as ethane (C2H6), acetylene (C2H2), and other natural gas elements (CO2, CH4) is of paramount importance and poses significant difficulty. We demonstrate such separations using an Al-MOF synthesised earlier as a non-porous material, but herein endowed with hierarchical porosity created under microwave conditions in an equimolar water/ethanol solution. The material possessing a large surface area (793 m2 g-1) exhibits an excellent uptake capacity for major industrial hydrocarbons in the order of C2H2 > C2H6 > CO2 > C2H4 > CH4 under ambient conditions. It shows an outstanding dynamic breakthrough separation of ethylene (C2H4) not only for a binary mixture (C2H6/C2H4) but also for a quaternary combination (C2H4/C2H6/C2H2/CO2 and C2H4/C2H6/C2H2/CH4) of varying concentrations. The detailed separation/purification mechanism was unveiled by gas adsorption isotherms, mixed-gas adsorption calculations, selectivity estimations, advanced computer simulations such as density functional theory (DFT), grand canonical Monte Carlo (GCMC) and ab initio molecular dynamics (AIMD), and stepwise multicomponent dynamic breakthrough experiments.

Multicolour lanthanide(III) porous 1D coordination polymers: tunable wide spectrum emission and efficient CuII sensing.

Five isostructural 1D porous coordination polymers (PCPs) with a general formula of {[M(L)(DMF)(H2O)]·1.5H2O}n [M = TbIII (1), EuIII (2), YbIII (3), NdIII (4) and ErIII (5)] have been synthesized using a flexible tripodal organic linker (L) and characterized. TbIII (1) and EuIII (2) PCPs exhibit metal-based green and red emission, respectively, whereas YbIII (3), NdIII (4) and ErIII (5) PCPs show near-infrared (NIR) emission. Doping EuIII in 1 in a precisely controlled stoichiometric amount leads to different mixed lanthanide PCPs, {[Tb1-xEux(L)(DMF)(H2O)]·1.5H2O}n (1a-1f) that show tunable emission including that of bright white light. The PCPs decorated with Lewis basic -O- binding sites make them potential candidates for the binding and selective sensing of traces of CuII ions, and this is illustrated for PCP 2 (limit of detection = 0.69 ± 0.02 ppm). The photoluminescence of 2 can be recovered by the introduction of a chelating ligand ethylenediaminetetraacetic acid (EDTA) without any structural disintegration, indicating the potential of the lanthanide PCPs for future sensing applications.

An Electrically Conducting Li-Ion Metal-Organic Framework.

Metal-organic frameworks (MOFs) have emerged as an important, yet highly challenging class of electrochemical energy storage materials. The chemical principles for electroactive MOFs remain, however, poorly explored because precise chemical and structural control is mandatory. For instance, no anionic MOF with a lithium cation reservoir and reversible redox (like a conventional Li-ion cathode) has been synthesized to date. Herein, we report on electrically conducting Li-ion MOF cathodes with the generic formula Li2-M-DOBDC (wherein M = Mg2+ or Mn2+; DOBDC4- = 2,5-dioxido-1,4-benzenedicarboxylate), by rational control of the ligand to transition metal stoichiometry and secondary building unit (SBU) topology in the archetypal CPO-27. The accurate chemical and structural changes not only enable reversible redox but also induce a million-fold electrical conductivity increase by virtue of efficient electronic self-exchange facilitated by mix-in redox: 10-7 S/cm for Li2-Mn-DOBDC vs 10-13 S/cm for the isoreticular H2-Mn-DOBDC and Li2-Mg-DOBDC, or the Mn-CPO-27 compositional analogues. This particular SBU topology also considerably augments the redox potential of the DOBDC4- linker (from 2.4 V up to 3.2 V, vs Li+/Li0), a highly practical feature for Li-ion battery assembly and energy evaluation. As a particular cathode material, Li2-Mn-DOBDC displays an average discharge potential of 3.2 V vs Li+/Li0, demonstrates excellent capacity retention over 100 cycles, while also handling fast cycling rates, inherent to the intrinsic electronic conductivity. The Li2-M-DOBDC material validates the concept of reversible redox activity and electronic conductivity in MOFs by accommodating the ligand's noncoordinating redox center through composition and SBU design.

Unraveling the Effect on Luminescent Properties by Postsynthetic Covalent and Noncovalent Grafting of gfp Chromophore Analogues in Nanoscale MOF-808.

Here, we demonstrate mimicking of photophysical properties of native green fluorescent protein (gfp) by immobilizing the gfp chromophore analogues in nanoscale MOF-808 and further exploring the bioimaging applications. The two virtually nonfluorescent gfp chromophore analogues carrying different functionalities, BDI-AE (COOH/COOMe) and BDI-EE (COOMe/COOMe) were immobilized in nanosized MOF-808 via postsynthetic modification. An 1H NMR and IR study confirms that BDI-AE was coordinated in NMOF-808, whereas BDI-EE was just noncovalently encapsulated. Interestingly, the extremely weakly fluorescent monomers BDI-AE and BDI-EE (QY = 0.01-0.03%, lifetime = 0.01-0.03 ns) showed a 102-fold increase in quantum efficiency with a significantly longer excited-state lifetime (QY = 1.8-5.6%, lifetime 0.89-1.49 ns) after immobilization in the NMOF-808 scaffold. Moreover, BDI-AE@MOF-808 has 4 times higher quantum efficiency as well as longer excited-state lifetime in comparison to BDI-EE@NMOF-808 due to the rigidity imposed in the chromophore upon coordination with Zr4+ in the former case. Further, a cell viability test performed for BDI-AE@NMOF-808 in HeLa cells confirmed the nontoxic nature of the material and, more importantly, bioimaging applications have also been explored successfully.

Modulating Hierarchical Micro/Mesoporosity by a Mixed Solvent Approach in Al-MOF: Stabilization of MAPbBr3 Quantum Dots.

Various hierarchical micro/mesoporous MOFs based on {[Al(µ-OH)(1,4-NDC)]⋅H2 O} (MOF1) with tunable porosities (pore volume and surface area) have been synthesized by assembling AlIII and 1,4-NDC (1,4-naphthalenedicarboxylate) under microwave irradiation by varying water/ethanol solvent ratio. Water/ethanol mixture has played a crucial role in the mesopore generation in MOF1M25 , MOF1M50 , and MOF1M75 , which is achieved by in situ formation of water/ethanol clusters. By adjusting the ratio of water/ethanol, the particle size, surface area and micro/mesopore volume fraction of the MOFs are controlled. Furthermore, reaction time plays a critical role in mesopore formation as realized by varying reaction time for the MOF with 50 % ethanol (MOF1M50 ). Additionally, hierarchical MOF (MOF1M50 ) has been used as a template for the stabilization of MAPbBr3 (MA=methylammonium) perovskite quantum dots (PQDs). MAPbBr3 PQDs are grown inside MOF1M50 , where mesopores control the size of PQDs which leads to quantum confinement.

Mixed Anionic and Cationic Redox Chemistry in a Tetrathiomolybdate Amorphous Coordination Framework.

We report the electrochemistry of a hitherto unexplored Na2 MoS4 phase as a conversion electrode material for Na- and Li-ion batteries. The material adopts an amorphous coordination polymer structure with mixed Mo and S valences. XPS and XRD analysis reveal a complex interplay between Mo and S redox chemistry, while excluding the formation of free sulfur, lithium sulfide, or other crystalline phases. Na2 MoS4 behaves as a mixed ionic-electronic conductor, with electronic conductivity of 6.1×10-4  S cm-1 , that permits carbon-free application in an electrochemical cell. A reversible capacity of up to 500 mAh g-1 was attained, corresponding to a five-electron redox exchange, with species ranging from (highest oxidized state) to 5 MoS4 > (lowest oxidized state). This study emphasizes the excellent charge-storage performances of Na2 MoS4 for Li- or Na-ion batteries, and enriches the emerging library and knowledge of sulfide phases with mixed anionic and cationic redox properties.

Stabilization of MAPbBr3 Perovskite Quantum Dots on Perovskite MOFs by a One-Step Mechanochemical Synthesis.

We report a one-step, solvent-free, green approach for the mechanochemical stabilization of hybrid organic-inorganic lead halide (MAPbBr3) perovskite quantum dots (PQDs) within perovskite metal-organic frameworks (MOFs) [MA-M(HCOO)3] [M = Mn and Co; MA = methylammonium (CH3NH3+)]. The perovskite MOF acts as a template and source of MA cations for growing and stabilizing hybrid PQDs. The synthesis of the composite has been carried out mechanochemically, without the use of any external reagents by simply grinding the perovskite MOF with PbBr2. MAPbBr3@MA-Mn(HCOO)3 composite shows high chemical stability in several solvents. Its excellent processability has been demonstrated by using it as an electrode material which shows photoelectrochemical activity in the presence of light.