High-spin States Research Articles

Facile Approach for the Fabrication of Vapor Sensitive Spin Transition Composite Nanofibers

In this work polymer nanofibers were functionalized by incorporation of the spin transition (ST) compound [Fe(H2btm)2(H2O)2]Cl2 (FeH2btm) (H2btm = di(1H‐tetrazol‐5‐yl)methane). FeH2btm is an interesting compound due to its ability to reversibly and sensitively switch between high spin (HS) and low spin (LS) state when exposed to common volatile compounds (VOC) like ammonia and methanol. By using polyvinylidene fluoride (PVDF) as the main compound, inhibiting interactions between the complex and polymer were minimized. By using UV‐Vis spectroscopy, the visible and reversible switching between HS and LS state when exposed to an ammonia or hydrochloric acid atmosphere was confirmed. Powder X‐Ray diffraction (PXRD), scanning electron microscopy (SEM) and energy dispersive X‐Ray spectroscopy (EDX) show a homogenous distribution of FeH2btm with no major crystalline accumulations and a mean fiber diameter of 106 ± 20 nm. The composite fiber has a similarly high thermal stability as the pure FeH2btm, as shown by thermogravimetric analysis (TGA). Mössbauer spectroscopy indicates an incomplete spin transition after exposition to ammonia. This could be due to low permeability of the VOC into the composite fiber.

Tuning the Electronic And Transport Properties of CaMoO4 Nanofibers with High-Spin Ni for Efficient and Stable Supercapacitors.

Calcium molybdate (CaMoO4) has recently garnered considerable attention for supercapacitors due to its stable crystal structure and cost-effective preparation. However, CaMoO4 prepared by traditional processes still suffered from insufficient electrochemical active sites and poor electrical conductivity so far, thus leading to the performance of CaMoO4-based supercapacitors being inferior to the state-of-the-art ones. CaMoO4 nanofibers with a high specific surface area exhibit great potential for supercapacitors due to their ability to offer increased charge storage. Herein, mesoporous CaMoO4 nanofibers anchored with Ni nanoparticles were fabricated via electrospinning combined with subsequent thermal treatment. Density functional theory calculation and UV-vis spectrophotometer results show that high-spin state Ni nanoparticles can tune the electronic structure of CaMoO4 nanofibers, decreasing the band gap by about 0.67 eV. Electron paramagnetic resonance (EPR) studies imply that Ni doping influences the electronic structure by reducing the oxygen vacancy concentration and introducing hyperfine structures associated with Ni spins. These can result in higher power and energy density in supercapacitors. As a result, a specific capacitance of 1253.7 F·g-1 at a current density of 0.5 A·g-1 and an 86% retention rate after 2000 cycles at a higher current density of 5 A·g-1 have been achieved for Ni0.25Ca0.75MoO4-based supercapacitor. Furthermore, an asymmetric supercapacitor (ASC) device with the optimized CaMoO4/Ni//AC structure has been demonstrated with the energy density of 49.43 Wh·kg-1 and power density of 2700 W·kg-1, thus enabling lightening a red light-emitting diode. The current strategy might pave the way for CaMoO4 for practical applications for high-power supercapacitors.

Chromium Complex of Macrocyclic Ligands as Precursor for Nitric Oxide Release: A Theoretical Study.

Our research on the chromium complex of macrocyclic ligands as a precursor for nitric oxide release makes a significant contribution. We detailed the analysis of nitrito chromium complexes, specifically trans-[M(III)L1-5(ONO)2]+, M=Cr(III) and L1-L5represent different ligands: L1=1,4,8,11-tetraazacyclotetradecane, L2= (5,7-dimethyl-6-benzylcyclam), L3=(5,7-dimethyl-6-anthracylcyclam), L4= (5,7-dimethyl-6-(p-hydroxymethylbenzyl)-1,4, 8,11-cyclam) and L5= (5,7-dimethyl-6-(1¢-methyl-4´-(1"-carboxymethylpyrene) benzyl)-1,4,8,11-tetraazacyclotetradecane). Our objective is to comprehensively understand the mechanism of NO release and identify the key factors influencing NO delivery. The optimized structure of the complexes at spin states S = 1/2 or 3/2 indicates a decrease in the Cr(III)-O bond length (1.669-1.671 Å) along with an increase in the Cr(III)O-NO bond length (2.735 - 2.741 Å), which facilitates the release of NO. Furthermore, there is a significant change in the bond angle (Cr-O-NO), from 120.4° to 116.9°, with respect to S=3/2, thus enlarging theO-NO bond and supporting the β-cleavage of NO from the complex. The calculated activation energy for the complexes reflects the energy difference between the low-spin doublet and high-spin quartet state due to spin crossover (SCO). Moreover, the Natural Transition Orbitals (NTOs) confirm the involvement of a hole-particle in the excitation. Additionally, TD-DFT reveals the pendant chromophore's role in generating NO, as the chromophore antenna effectively enhances light absorption.

Symmetry Breaking in a Triferrous Extended Metal Atom Chain.

Semilocal and random phase approximation (RPA) density functional theory (DFT) and complete active space (CASSCF + NEVPT2) methodologies were applied to investigate a new class of extended metal atom chain (EMAC) complexes. A novel triferrous complex has been synthesized recently that does not utilize the usual 2,2'-dipyridylamine (dpa) ligand framework, which essentially always results in a tetragonal coordination environment and general formula M3(dpa)4X2, where X is an anion. Instead, the triferrous complex utilizes a dianionic, 2,6-bis(trimethylsilylamido)pyridine ligand (L2-) resulting in the formation of trigonal complexes with general formula Fe3L3. To better understand the electronic structure of this complex, calculations were utilized to explore the experimentally isolated Fe3L3, and a smaller theoretical complex, in order to compare and contrast with the traditional dpa-based EMACs. Due to the absence of anionic, axial ligands, the sigma nonbonding orbitals formed from the metal d orbitals are lower in energy than in the dpa complexes, and compete with the pi bonding orbitals for occupation in the Fe3L3 complex. While the idealized geometry of these complexes is D3h, a helical distortion of the ligands and subsequent electronic symmetry breaking due to Jahn-Teller distortions are predicted utilizing both semilocal and RPA DFT methods, ending in a C2 structure that closely matches the reported crystal structure. Predicted Mössbauer isomer shifts and ultraviolet/visible (UV/vis) spectra also agree with the experimental data available in the literature. Magnetic coupling constants also indicate ferromagnetic coupling between nearest neighbor irons. Two-dimensional (2D) potential energy surfaces were calculated for a range of fixed Fe-Fe bond lengths, revealing a flat potential energy surface over a wide range of Fe-Fe bond lengths and verifying the ability of RPA to act as a higher-level check on semilocal DFT results. In order to verify the predicted high-spin ground state, CASSCF + NEVPT2 was applied to selected molecular configurations and confirmed the predictions made by DFT. These calculations shed light on the physical ground state electron configuration of Fe3L3 and correlate this electronic configuration with the available experimental data.

Spectroscopic study of Mo97, Mo99 , and Mo101

Excited states of the molybdenum isotopes Mo4297,99,101 have been populated in two experiments which used fusion-fission and binary grazing reactions to populate yrast states of the nuclei of interest. In the first experiment, the GASP array of escape-suppressed Ge detectors was used to detect γ rays from fusion-fission products initiated by the interaction of a 230-MeV beam of S36 ions with a thick target of Yb176. In the multinucleon transfer experiment, a 530-MeV beam of Zr96 ions was incident on a thin Sn124 target; projectile-like ejectiles were detected and identified using the PRISMA magnetic spectrometer and their associated γ rays were detected using the CLARA array of escape-suppressed Ge detectors. In Mo99, the previously known positive-parity νd5/2 decay sequence was extended to spin (25/2+) while, in Mo101, a similar, but hitherto unobserved νg7/2 positive-parity decay sequence was established to spin (27/2+). In Mo99 and in Mo101, previously observed νh11/2 negative-parity decay sequences were also observed to spin 27/2−. Although the observed decay sequences in Mo97 have not been extended beyond the results of earlier work, a disagreement in the published level structure of the h11/2 band has been resolved. The observed positive-parity decay sequences have been compared with the results of state-of-the-art shell-model calculations; the general features of the energy spectrum of excited states of Mo97, Mo99, and Mo101 are reproduced, but not in detail. The experimental energies of the negative-parity states of Mo99 and Mo101 are reasonably well reproduced in particle-rotor (PRM) calculations. For Mo97, better agreement with the high-spin states was obtained when the core in the PRM calculations was treated in a variable moment of inertia approach. For the νh11/2 negative-parity decay sequences of the three isotopes studied here, model-dependent evidence is presented for nuclear shape changes with increasing neutron number. Published by the American Physical Society 2024

Prediction by DFT and Docking Calculations of a Series of Hypothetical 3d Transition Element Isostructural Complexes [M(hfac)2(TTF)2]: A Comparative Study

AbstractThe study aims to predict and compare the structural, electronic, conductivity, and biological properties of a series of 3d transition element complexes with those of the previously studied isostructural copper complex [Cu(hfac)2(TTF)2][PF6]2 (TTF: tetrathiafulvalene, hfac: hexafluoroacetylacetonate). Because transition metals hold open electronic shells, all possible spin states for all divalent compounds have to be considered in order to determine the most stable configurations. These configurations are those corresponding to the highest spin state (5 for Mn, 4 for Fe, 3 for Co, 2 for Ni, 1 for Cu, and 0 for Zn). However, the configurations with the smallest gap are Mn(3) and Co(1), suggesting that these are the most conductive complexes. A significant metal–ligand charge transfer is observed for both Mn and Co complexes. Antifungal (CYP121 (PDB: 2IJ7) and CYP51 (PDB: 1EA1)) and antibacterial (Escherichia coli (PDB: 1KZN)) properties of the compounds studied were evaluated by molecular docking; the results obtained reveal that the following complexes show significant activity: Zn(hfac)2(TTF)2] [PF6]2 (−8.9 kcal/mol), Ni(hfac)2(TTF)2] [PF6]2 (−7.8 kcal/mol), and Cu(hfac)2(TTF)2] [PF6]2 (−8.2 kcal/mol).

Improving Predictions of Spin-Crossover Complex Properties through DFT Calculations with a Local Hybrid Functional.

We conducted a study on the performance of the local hybrid exchange-correlation functional PBE0r for a set of 95 experimentally characterized iron spin-crossover (SCO) complexes [Vennelakanti, V.; J. Chem. Phys. 2023, 159, 024120]. The PBE0r functional is a variant of PBE0 where the exchange correction is restricted to on-site terms formulated on the basis of local orbitals. We determine the free parameters of the PBE0r functional against the experimental data and other hybrid functionals. With a Hartree-Fock (HF) exchange factor of 4%, the PBE0r functional accurately reproduces the electronic and free-energy trends predicted in prior DFT studies for these 95 complexes by using the B3LYP functional. Larger values of HF exchange stabilize high-spin states. The PBE0r-predicted bond lengths tend to exceed the experimental bond lengths, although bond lengths are less sensitive to HF exchange than in global hybrids. The predicted SCO transition temperatures T1/2 from PBE0r correlate moderately with the experimental transition temperatures, showing a slight improvement compared to the previous modB3LYP-predicted T1/2. This study suggests that the PBE0r functional is computationally cost-effective and offers the possibility of simulating larger complexes with accuracy comparable to global hybrid functionals, provided the HF-exchange parameter is carefully optimized.

Changing magnetic ground state by an electric field in a single-layer FeCl2

Abstract Employing the electric field has been performed to investigate the magnetic ground state in a single-layer iron dichloride (FeCl2). We provided some lattice parameters to see the ground state dependency on the electric field. To minimize the computational time, we applied the generalized Bloch theorem via density functional theory to avoid the supercell approach. As we varied the electric field, we saw the magnetic transition for some lattice parameters. In addition, the magnetic moments were nearly stable for all those states, indicating the high spin state. As a concluding remark, employing the electric field is very useful to manipulate the ground state that can be applied to magnetism-based nanotechnology.

The Effect of the Surrounding Matrix on Spin Transition Nanoparticles: How Shell Characteristics Alter Core Elastic Properties in Core‐Shell Particles

A surrounding matrix is known to alter nanoparticle spin transitions, the solid state structural phase changes associated with transitions between high spin (HS) and low spin(LS) states. To better quantify how the spin transition solid and surrounding matrix interact, several series of core‐shell particles were prepared based on RbxCo[Fe(CN)6]z∙nH2O, RbCoFe‐PBA, as spin transition core with isostructural shells of different compositions and thicknesses. Synchrotron PXRD through the thermal high HS to LS, the LS to photoexcited high spin (PXHS), and thermal PXHS to LS transitions, show the activation energy is lowered as shells become thicker and stiffer. Calorimetry data coupled with transition state theory analysis indicate the core stiffens in the core‐shell particles relative to the uncoated particles. The conclusion is supported by microstrain analysis that shows stiffer shells limit the extent to which the core distorts as individual sites transition, leading to the lower activation energy. Finally, differences in lattice mismatch with different shell materials are shown to alter the mechanism by which the transition progresses.

Spin-dependent activity of cobalt contained hydroxy double perovskite for efficient antibiotic removal via peroxymonosulfate activation

Cobalt-containing catalysts exhibit good performance in the advancement of efficient catalytic oxidation reactions. However, achieving an optimal balance between reaction kinetics and adsorption, usually governed by variable spin states of Co ions, to enhance the performance remains a significant challenge. This study aims to develop a convenient compositional tuning strategy to achieve such balance in stable CoxZn1-xSn(OH)6 perovskite hydroxides. We systematically investigate the effect of varying spin state on a chosen representative catalytic oxidation reaction, namely peroxymonosulfate activation and tetracycline hydrochloride removal. The magnetic properties analysis reveal that the content of octahedral Co2+ ions with high-spin state increases with Co content (x) and reaches 59.5 % in Co0.5Zn0.5Sn(OH)6. Experimental results and DFT calculations reveal that the spin states transition of Co2+ ions enhance the interaction between Co and O atoms. This enhanced interaction not only improves the reactivity due to the formation of highly covalent Co-OH bonds that serve as catalytically activated charge transfer channels, but also optimizes the suitable adsorption energy of PMS molecules at −3.52 eV for Co0.5Zn0.5Sn(OH)6. Consequently, Co0.5Zn0.5Sn(OH)6 shows superior catalytic activity, achieving nearly 100 % antibiotic removal efficiency within just 10 min, surpassing previously reported catalysts. These findings underscore the potential of compositional tuning spin states of transition metal ions in advancing oxidation processes and designing innovative catalysts.

Evidence of Cooperative Effects for the Fe(phen)2(NCS)2 Spin Crossover Molecular Complex in Polyaniline Plus Iron Magnetite.

The spin crossover complex Fe(phen)2(NCS)2 and its composite, Fe(phen)2(NCS)2, combined with the conducting polymer polyaniline (PANI) plus varying concentrations of iron magnetite (Fe3O4) nanoparticles were studied. A cooperative effect is evident from the hysteresis width in the plot of magnetic susceptibility multiplied by temperature versus temperature (χmT versus T) for Fe(phen)2(NCS)2 with PANI plus varying concentrations of Fe3O4 nanoparticles. The hysteresis width in the composites vary no more than 2 K with respect to the pristine Fe(phen)2(NCS)2 spin crossover crystallites despite the fact that there exists a high degree of miscibility of the Fe(phen)2(NCS)2 spin crossover complex with the PANI. The Fe3O4 nanoparticles in the Fe(phen)2(NCS)2 plus PANI composite tend to agglomerate at higher concentrations regardless of the spin state of Fe(phen)2(NCS)2. Of note is that the Fe3O4 nanoparticles are shown to be antiferromagnetically coupled with the Fe(phen)2(NCS)2 when Fe(phen)2(NCS)2 is in the high spin state.

Mononuclear high-spin iron(III) phthalocyanines

2,9(or 10),16(or 17), 23(or 24)-Tetradecyloxycarbonylphthalocyaninatoiron, FeTDPc, and 2,3,9,10,16,17,23,24-octadecyloxycarbonylphthalocyaninatoiron, FeODPc, were synthesized and characterized. These compounds seem to be in trivalent iron high-spin state in solvents such as chloroform, dichloromethane, benzene, and chlorobenzene, although their counter anion could not be detected by elemental analyses. They react with strong bases such as pyridine and imidazoles to form their mono- and subsequently their di-base complexes with formation constant of >106 and < 200 dm3 mol−1, respectively, in dichloromethane at 20 °C. The resultant mono-adducts appear to be trivalent iron low-spin while the di-base adducts are bivalent iron low-spin state complexes. The addition of ca. 10–30 equivalent of tetrabutylammonium-chloride or -bromide (electrolyte) to the solution containing FeTDPc or FeODPc, causes their spin-state change from iron(III) high to low-spin state. In a solid power state, however, both FeTDPc and FeODPc exist as a mixture of high-spin iron(III)- and intermediate-spin iron(II) species. Strangely, when these compounds are dissolved in polystyrene, i.e. each molecules are isolated from each other, the signals originated from the iron(II) component disappear.

Spin Manipulation of Heterogeneous Molecular Electrocatalysts by an Integrated Magnetic Field for Efficient Oxygen Redox Reactions.

Understanding the spin-dependent activity of nitrogen-coordinated single metal atom (M-N-C) electrocatalysts for oxygen reduction and evolution reactions (ORR and OER) remains challenging due to the lack of structure-defined catalysts and effective spin manipulation tools. Herein, both challenges using a magnetic field integrated heterogeneous molecular electrocatalyst prepared by anchoring cobalt phthalocyanine (CoPc) deposited carbon black on polymer-protected magnet nanoparticles, are addressed. The built-in magnetic field can shift the Co center from low- to high-spin (HS) state without atomic structure modification, affording one-order higher turnover frequency, a 50% increased H2O2 selectivity for ORR, and a ≈4000% magnetocurrent enhancement for OER. This catalyst can significantly minimize magnet usage, enabling safe and continuous production of a pure H2O2 solution for 100 h from a 100 cm2 electrolyzer. The new strategy demonstrated here also applies to other metal phthalocyanine-based catalysts, offering a universal platform for studying spin-related electrochemical processes.

Perovskite-Like Carbodiimides AB(NCN)3: Synthesis and Characterization of MnHf(NCN)3 and FeHf(NCN)3.

Two novel ternary air-stable transition-metal carbodiimides, MnHf(NCN)3 and FeHf(NCN)3, were synthesized via solid-state metathesis using either ZnNCN or Na2NCN as the carbodiimide source and the corresponding binary metal chlorides. These two phases are the first examples of transition-metal carbodiimides with an AB(NCN)3 composition, akin to ubiquitous ABO3 perovskite oxides. The crystal structure of MnHf(NCN)3 was determined and refined from powder X-ray diffraction (XRD) data in the non-centrosymmetric space group P6322 allowing for chirality, the assignment of which is supported by second-harmonic generation (SHG) measurements. FeHf(NCN)3 was found to crystallize isotypically, and the presence of iron(II) in a high spin state was confirmed by 57Fe Mößbauer spectroscopy. The structures are revealed to be NiAs-derived and can be described as a hexagonal stack of NCN2- anions with metal cations occupying 2/3 of the octahedral voids. Both IR spectroscopic measurements and DFT calculations agree that the NCN2- unit is a bent carbodiimide with C2v symmetry, necessary to account for the size difference present in such a vacancy-ordered structure. Magnetic studies reveal predominantly strong antiferromagnetic interactions but no long-range order between the paramagnetic Mn2+ centers, likely due to the dilution of Mn2+ over the octahedral sites or perhaps even due to some degree of magnetic frustration. The optical and electrochemical properties of MnHf(NCN)3 were then studied, revealing a wide band gap of 3.04 eV and p-type behavior.

1,1'-Biolympicenyl: A Stable Non-Kekulé Diradical with a Small Singlet and Triplet Energy Gap.

Dimerization of delocalized polycyclic hydrocarbon radicals is a simple and versatile method to create diradicals with tailored electronic structures and accessible high-spin states. However, the synthesis is challenging, and the stability issue of the diradicals remains a concern. In this study, we present the synthesis of a stable non-Kekulé 1,1'-biolympicenyl diradical 1 using a protection-oxidation-protection strategy. Diradical 1 demonstrated exceptional stability, with a solution half-life time exceeding 3.5 years and a solid state thermal decomposition temperature above 300 °C. X-ray crystallographic analysis revealed its intersected molecular structure and tightly bound dimer configuration. A singlet ground state with a small singlet-triplet energy gap is consistently identified using electron paramagnetic resonance (EPR) and a superconducting quantum interference device (SQUID) in a rigid matrix, and the triplet state is thermally accessible at room temperature. The solution phase properties were systematically examined through EPR, absorption spectroscopy, and cyclic voltammetry, revealing a rotational motion in the slow-motion regime and multistage redox characteristics. This study presents an efficient synthetic and stabilization strategy for organic diradicals, enabling the development of various high-spin functional materials.

Electrical Sensing of Molecular Spin State Switching in a Spin Crossover Complex Using an Organic Field‐Effect Transistor

AbstractAn organic semiconductor – spin crossover polymer composite heterostructure is fabricated, and it is integrated into an organic field‐effect transistor (OFET) with the aim to achieve electrical sensing of molecular spin state switching events. The OFETs display ≈50–70% increase in drain‐source current intensity when going from the low spin (LS) to the high spin (HS) state. This phenomenon is reversible without apparent fatigue and the application of a gate voltage significantly enhances the sensing sensitivity. Capacitance measurements and finite element calculations allow identifying mechanical stress, induced by the spin state switching, at the origin of the transistor response. These results open up appealing perspectives for the integration of spin crossover molecules into technological applications, such as soft robotics .

Structure and spin of the low- and high-spin states of Fe2+(phen)3 studied by x-ray scattering and emission spectroscopy.

The structure and spin of photoexcited Fe2+(phen)3 in water are examined by x-ray scattering and x-ray emission spectroscopy with 100 ps time resolution. Excitation of the low-spin (LS) ground state (GS) to the charge transfer state 1MLCT* leads to the formation of a high-spin (HS) state that returns to the GS in 725 ps. Density functional theory (DFT) predicts a Fe-N bond elongation in HS by 0.19 Å in agreement with the scattering data. The angle between the ligands increases by 5.4° in HS, which allows the solvent to get 0.33 Å closer to Fe in spite of the expansion of the molecule. The rise in solvent temperature from the return of photoproducts to the GS is dominated by the formation dynamics of HS, 1MLCT* → HS, which is followed by a smaller rise from the HS → GS transition. The latter agrees with the 0.61 eV energy gap E(HS)-E(LS) calculated by DFT. However, the temperature rise from the 1MLCT → HS transition is greater than expected, by a factor of 2.1, which is explained by the re-excitation of nascent HS* by the 1.2 ps pump pulse. This hypothesis is supported by optical spectroscopy measurements showing that the 1.2 ps long pump pulse activates the HS* → 5MLCT* channel, which is followed by the ultrafast return to HS* via intersystem crossing. Finally, the spins of the photoproducts are monitored by the Kβ emission and the spectra confirm that the spins of LS and HS states are 0 and 2, respectively.

Electronic and magnetic phase diagram of Sr2FeO4 at high pressure: A synchrotron Mössbauer study

Transition metal (TM) oxides with high oxidation state TM ions exhibit a variety of unconventional electronic and magnetic states owing to electron correlations effects combined with highly covalent TM–O bonding. Here, we have studied the pressure dependence of electronic state and magnetism of the K2NiF4-type iron(IV) oxide Sr2FeO4 up to 89 GPa by temperature and magnetic field dependent energy-domain synchrotron Mössbauer spectroscopy and derived a (P,T) magnetic phase diagram. Considering also previous resistance studies [Rozenberg , ] several magnetic and electronic regimes with increasing pressure can be identified. Near 7 GPa, the insulating cycloidal antiferromagnetic low-P state is transformed into a semiconducting ferromagnetic state and the magnetic ordering temperature Tm increases from 55 K at ambient pressure to about 100 K at 13 GPa. Between 18 and about 50 GPa the system is ferromagnetic and metallic (FMM) with a strong rise of Tm to above room temperature (RT). Contrary to a recent theoretical study [Kazemi-Moridani , ], the FMM state is attributed to a high-spin t2g3eg1 electronic state with itinerant eg coupled to more localized t2g electrons. Between 50 and 89 GPa a doublet with large quadrupole splitting in the RT Mössbauer spectra indicates a partial high-spin to low-spin (t2g4) transition leading to a decrease in Tm again. The general features of the (P,T) phase diagram of Sr2FeO4 are comparable to those of other simple and A-site ordered iron(IV) perovskite-related oxides with the peculiarity that Sr2FeO4 adopts an insulating state without charge disproportionation of Fe4+ in the low-P region. The high-pressure behavior of Sr2FeO4 and other iron(IV) oxides may be relevant for exploring the role of Hund's physics in multiorbital systems and contributing to the understanding of the electronic situation in unconventional superconductors such as La3Ni2O7 and Sr2RuO4. Published by the American Physical Society 2024

Metal–Organic Frameworks with Axial Cobalt–Oxygen Coordination Modulate Polysulfide Redox for Lithium–Sulfur Batteries

AbstractAlthough the ultrahigh theoretical energy density and cost‐effectiveness, lithium–sulfur (Li‐S) batteries suffer from sluggish conversion kinetics and the shuttling effect of soluble lithium polysulfides (LiPSs). Herein, conductive hexagonal cobalt‐organic framework (Co‐HTP) nanosheets are anchored in situ on carboxyl graphene (CG) substrates and serve as host catalysts to modulate the polysulfide redox. Substantial characterizations identify that the local coordination environment of the quadrilateral Co–N4 units transforms into an asymmetric penta‐coordinated O–Co–N4 with axial Co─O coordination, which triggers spin polarization and remarkable electron delocalization of Co 3d orbital. The higher spin state and lower local electron density of the O–Co–N4 sites induce more active electronic states in Co‐HTP/CG and facilitate orbital hybridization with polysulfides to form more stable bond orders. Such optimized electronic structure significantly accelerates redox kinetics and enhances the adsorption strength of polysulfides. These merit the lithium–sulfur battery based on Co‐HTP/CG with a high reversible capacity, impressive rate capability, and prolonged cycling performance over 500 cycles. This work will enrich the design philosophy of modulating the spintronic structure of electrocatalysts for advanced Li–S batteries and beyond.

Production of Lactic Acid via Catalytic Transfer Dehydrogenation of Glycerol Catalyzed by Base Metal Salt Ferrous Chloride and Its NNN Pincer-Iron Complexes.

NNN-Bis(imino) pyridine-based pincer-Fe(II) complexes with an expected trigonal bipyramidal (TBP) geometry equilibrated to a rearranged ion pair of an octahedral dicationic Fe complex containing two bis(imino)pyridine ligands that are neutralized by a tetrahedral dianionic-[FeCl4]2-. Single-crystal X-ray diffraction (SCXRD), high-resolution mass spectrometry (HRMS), and UV-visible (UV-vis) studies suggested that the equilibrium was dictated by the sterics of the R group on the imine N, with the less-crowded groups tilting the equilibrium to the ion pair and the bulky ones favoring the TBP geometry. Electron paramagnetic resonance (EPR) and Evan's magnetic moment measurements indicated that the complexes were paramagnetic with Fe(II) in a high-spin state. In solution, over a period of 7 days, these Fe(II) complexes oxidized to a mixture of low-spin and high-spin Fe(III) species. These pincer-Fe(II) were found to be highly active toward the transformation of biodiesel waste glycerol to value-added lactic acid (LA). Particularly, (Ph2NNN)FeCl2 (0.1 mol %) gave 91% LA with a 99% selectivity at 140 °C using 1.2 equiv of NaOH. With 0.0001 mol % (Ph2NNN)FeCl2, very high turnovers (74% LA, 98% selectivity, 740 000 turnover number (TON) at 4405 turnovers per hour (TOs/h)) were obtained after 7 days. EPR indicated Fe(III) species to be the active catalyst, a few of which were detected by HRMS. Experiments with Hg are suggestive of the mostly homogeneous molecular nature of the catalyst with a minor contribution from heterogeneous Fe nanoparticles.