[Fe(bppCOOH)2]2+

Four alkyl chains and cyclohexane modified FeII complexes [Fe(Ln)(L’)](ClO4)2⋅solv (n=1, 2, 3, 4) were synthesized and characterized. X‐ray diffraction study showed that these complexes were constituted by asymmetric mononuclear FeII entities, incorporating alkyl‐chain‐modified bppCOOH (2,6‐bis(1H‐pyrazol‐1‐yl)isonicotinic acid) ligands and 6,6’’‐2,6‐dimethoxyphenyl‐substituted terpy ligand (L’). Magnetic susceptibility measurements revealed that complexes 1, 2, and 3 were in the high spin state across the measured temperature range, whereas complex 4 displayed an incomplete spin crossover phenomenon, with a transition temperature (T1/2) at 240 K. Investigations into variable‐temperature structure and magneto‐structural correlations revealed that the integration of alkyl‐chain‐modified bipyridyl units fostered the π⋅⋅⋅π intra‐ and intermolecular interactions, contributing to distinct crystal stacking and spatial configurations in complex 4 when compared to its counterparts. These findings underscore the pivotal influence of intramolecular interactions on the FeII spin states and highlight the significance of designing flexible ligands for modulating spin‐crossover characteristics.

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The synthesis and magnetostructural characterization of [Fe(III)3(μ3-O)(H2O)3[Fe(II)(bppCOOH)(bppCOO)]6](ClO4)13·(CH3)2CO)6·(solvate) (2) are reported. This compound is obtained as a secondary product during synthesis of the mononuclear complex [Fe(II)(bppCOOH)2](ClO4)2 (1). The single-crystal X-ray diffraction structure of 2 shows that it contains the nonanuclear cluster of the formula [Fe(III)3(μ3-O)(H2O)3[Fe(II)(bppCOOH)(bppCOO)]6](13+), which is formed by a central Fe(III)3O core coordinated to six partially deprotonated [Fe(II)(bppCOOH)(bppCOO)](+) complexes. Raman spectroscopy studies on single crystals of 1 and 2 have been performed to elucidate the spin and oxidation states of iron in 2. These studies and magnetic characterization indicate that most of the iron(II) complexes of 2 remain in the low-spin (LS) state and present a gradual and incomplete spin crossover above 300 K. On the other hand, the Fe(III) trimer shows the expected antiferromagnetic behavior. From the structural point of view, 2 represents the first example in which bppCOO(-) acts as a bridging ligand, thus forming a polynuclear magnetic complex.

We investigate spin-state transitions in a series of 24 [FeII(bppX)2]2+ spin-crossover (SCO) complexes using density functional theory (DFT). The TPSSh/def2-TZVP approach demonstrates reasonable accuracy in predicting spin-state energetics compared to other functionals, though significant deviations persist in transition temperature (T 1/2) estimates. Temperature-dependent and quasi-harmonic corrections for low-frequency vibrational contributions to enthalpic and entropic terms yielded only marginal improvements. To improve T 1/2 prediction accuracy, we develop electronic descriptors based on effective fragment orbitals (EFOs) and their occupations, quantifying ligand σ-donation and π-acceptor characteristics that govern ligand field strength. Additionally, we introduce a resonance descriptor (R) derived solely from the effective atomic orbitals (eff-AOs) of isolated ligands. Our analysis reveals that electron-donating groups (EDGs) enhance π-electron density in the ligands while simultaneously reducing both σ-donor and π-acceptor capabilities, ultimately lowering the T 1/2 value. These descriptors perform reasonably well also for a set of 12 [FeII(pyboxX)2]2+ SCO complexes. This new methodology provides a computationally efficient framework for modulating spin-state properties in transition metal complexes, enabling rational design of SCO materials.

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Two new heteroleptic complexes [Fe(1bppCOOH)(3bpp-bph)](ClO4)2·solv (1·solv, solv = various solvents; 1bppCOOH = 2,6-bis(1H-pyrazol-1-yl)isonicotinic acid; 3bpp-bph = 2,6-bis(5-([1,1'-biphenyl]-4-yl)-1H-pyrazol-3-yl)pyridine) and [Fe(1bppCOOH)(1bppCOOEt)](ClO4)2·0.5Me2CO (2·0.5Me2CO, 1bppCOOEt = ethyl 2,6-bis(1H-pyrazol-1-yl)isonicotinate) were designed and prepared. The heteroleptic compound 1·solv was obtained by the combination of stoichiometric amounts of Fe(ClO4)2, 1bppCOOH, and 3bpp-bph, and it was designed to fine-tune the spin crossover (SCO) properties with respect to the previously reported homoleptic compound [Fe(1bppCOOH)2](ClO4)2. Indeed, the introduction of a new substituted 3bpp ligand induces a weaker ligand field in addition to promoting the formation of π···π and C-H···π intermolecular interactions through the biphenyl groups. For the desolvated counterpart 1, this results in a shift of the SCO curve toward room temperature and the observation of a 13 K hysteresis width. Besides, compound 2·0.5Me2CO, which represents the first example of a heteroleptic complex containing two 1bpp tridentate ligands, stabilizes the LS state at room temperature confirming the same trend observed for the corresponding homoleptic compounds. Interestingly, both 1 and 2·0.5Me2CO heteroleptic complexes exhibit photoswitchable properties when irradiating with a 523 nm laser at 10 K. Preliminary characterization of the deposited complexes on native SiO2 by X-ray absorption measurements suggests oxidation and decomposition of the complexes.

The synthesis of six 2,6-di(pyrazol-1-yl)pyridine derivatives bearing dithiolane or carboxylic acid tether groups is described: [2,6-di(pyrazol-1-yl)pyrid-4-yl]methyl (R)-lipoate (L1), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]ethyl (R)-lipoate (L2), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxy]ethyl (R)-lipoate (L3), N-([2,6-di(pyrazol-1-yl)pyrid-4-ylsulfanyl]-2-aminoethyl (R)-lipoamide (L4), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]acetic acid (L5) and 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]propionic acid (L6). The iron(ii) perchlorate complexes of all the new ligands exhibit gradual thermal spin-crossover (SCO) in the solid state above room temperature, except L4 whose complex remains predominantly high-spin. Crystalline [Fe(L6)2][ClO4]2·2MeCN contains three unique cation sites which alternate within hydrogen-bonded chains, and undergo gradual SCO at different temperatures upon warming. The SCO midpoint temperature (T1/2) of the complexes in CD3CN solution ranges between 208-274 K, depending on the functional group linking the tether groups to the pyridyl ring. This could be useful for predicting how these complexes might behave when deposited on gold or silica surfaces.

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Abstract Bistable spin‐crossover (SCO) complexes that undergo abrupt and hysteretic (ΔT 1/2) spin‐state switching are desirable for molecule‐based switching and memory applications. In this study, we report on structural facets governing hysteretic SCO in a set of iron(II)‐2,6‐bis(1H‐pyrazol‐1‐yl)pyridine) (bpp) complexes – [Fe(bpp−COOEt)2](X)2 ⋅CH3NO2 (X=ClO4, 1; X=BF4, 2). Stable spin‐state switching – T 1/2=288 K; ΔT 1/2=62 K – is observed for 1, whereas 2 undergoes above‐room‐temperature lattice‐solvent content‐dependent SCO – T 1/2=331 K; ΔT 1/2=43 K. Variable‐temperature single‐crystal X‐ray diffraction studies of the complexes revealed pronounced molecular reorganizations – from the Jahn‐Teller‐distorted HS state to the less distorted LS state – and conformation switching of the ethyl group of the COOEt substituent upon SCO. Consequently, we propose that the large structural reorganizations rendered SCO hysteretic in 1 and 2. Such insights shedding light on the molecular origin of thermal hysteresis might enable the design of technologically relevant molecule‐based switching and memory elements.

In the title complex, [Mn(C11H10N3O2)2]·2C7H4N2O6, the MnII atom has a disorted octahedral coordination formed by four N and two O atoms of two mer-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate ligands (DMPP). Each of the two symmetry-independent 3,5-dinitrobenzoic acid molecules is linked to the molecule of the complex via a hydrogen bond involving its carboxylic H atom and one of the DMPP ligands of the complex. However, in one of the DMPP ligands, the non-coordinated carbonyl O atom serves as the hydrogen-bond acceptor, whereas in the second ligand it is the Mn-coordinated O atom which is involved in the hydrogen bonding.

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A series of bis(pyrazol-1-yl)pyridine (1-BPP)-based iron(II) complexes bearing either a boronic acid group or boronic monoester groups, with the general formula [FeII(1-BPP)2](ClO4)2, have been synthesized and characterized in the solid...

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Molecular design of spin-crossover complexes relies on controlling the spin state of a transition metal ion by proper chemical modifications of the ligands. Here we report the first N,N'-disubstituted 2,6-bis(pyrazol-3-yl)pyridines (3-bpp) that, against the common wisdom, induce a spin-crossover in otherwise high-spin iron(II) complexes by increasing the steric demand of a bulky substituent, an ortho-functionalized phenyl group. As N,N'-disubstituted 3-bpp complexes have no pendant NH groups that make their spin state extremely sensitive to the environment, the proposed ligand design, which may be applicable to isomeric 1-bpp or other families of popular bi-, tri- and higher denticity ligands, opens the way for their molecular design as spin-crossover compounds for future breakthrough applications.

Two carboxyl-substituted iron(II) grids, one protonated, [Fe4(HL)4](BF4)4·4MeCN·AcOEt (1), and the other deprotonated, [Fe4(L)4]·DMSO·EtOH (2), where H2L = 4-{4,5-bis[6-(3,5-dimethylpyrazol-1-yl)pyrid-2-yl]-1 H-imidazol-2-yl}benzoic acid, were synthesized. Single-crystal X-ray structure analyses reveal that both complexes have a tetranuclear [2 × 2] grid structure. 1 formed one-dimensional chains through intermolecular hydrogen bonds between the carboxylic acid units of neighboring grids, while 2 formed two-dimensional layers stabilized by π-π-stacking interactions. 1 showed spin transition between the 3HS-1LS and 1.5HS-2.5LS states around 200 K, while 2 showed spin-crossover between the 4LS and 2LS-2HS states above 300 K. A modified indium-tin oxide (ITO) electrode was fabricated by soaking the ITO in a solution of 1. The resultant electrode showed reversible redox waves attributed to the original redox processes of iron(II)/iron(III).

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Abstract Four bis[2‐{pyrazol‐1‐yl}‐6‐{pyrazol‐3‐yl}pyridine] ligands have been synthesized, with butane‐1,4‐diyl (L 1), pyrid‐2,6‐diyl (L 2), benzene‐1,2‐dimethylenyl (L 3) and propane‐1,3‐diyl (L 4) linkers between the tridentate metal‐binding domains. L 1 and L 2 form [Fe2(μ−L)2]X4 (X−=BF4 − or ClO4 −) helicate complexes when treated with the appropriate iron(II) precursor. Solvate crystals of [Fe2(μ−L 1)2][BF4]4 exhibit three different helicate conformations, which differ in the torsions of their butanediyl linker groups. The solvates exhibit gradual thermal spin‐crossover, with examples of stepwise switching and partial spin‐crossover to a low‐temperature mixed‐spin form. Salts of [Fe2(μ−L 2)2]4+ are high‐spin, which reflects their highly twisted iron coordination geometry. The composition and dynamics of assembly structures formed by iron(II) with L 1−L 3 vary with the ligand linker group, by mass spectrometry and 1H NMR spectroscopy. Gas‐phase DFT calculations imply the butanediyl linker conformation in [Fe2(μ−L 1)2]4+ influences its spin state properties, but show anomalies attributed to intramolecular electrostatic repulsion between the iron atoms.

We here report the synthesis of the homoleptic iron(II) N-heterocyclic carbene (NHC) complex [Fe(miHpbmi)2](PF6)4 (miHpbmi = 4-((3-methyl-1H-imidazolium-1-yl)pyridine-2,6-diyl)bis(3-methylimidazol-2-ylidene)) and its electrochemical and photophysical properties. The introduction of the π-electron-withdrawing 3-methyl-1H-imidazol-3-ium-1-yl group into the NHC ligand framework resulted in stabilization of the metal-to-ligand charge transfer (MLCT) state and destabilization of the metal-centered (MC) states. This resulted in an improved excited-state lifetime of 16 ps compared to the 9 ps for the unsubstituted parent compound [Fe(pbmi)2](PF6)2 (pbmi = (pyridine-2,6-diyl)bis(3-methylimidazol-2-ylidene)) as well as a stronger MLCT absorption band extending more toward the red spectral region. However, compared to the carboxylic acid derivative [Fe(cpbmi)2](PF6)2 (cpbmi = 1,1′-(4-carboxypyridine-2,6-diyl)bis(3-methylimidazol-2-ylidene)), the excited-state lifetime of [Fe(miHpbmi)2](PF6)4 is the same, but both the extinction and the red shift are more pronounced for the former. Hence, this makes [Fe(miHpbmi)2](PF6)4 a promising pH-insensitive analogue of [Fe(cpbmi)2](PF6)2. Finally, the excited-state dynamics of the title compound [Fe(miHpbmi)2](PF6)4 was investigated in solvents with different viscosities, however, showing very little dependency of the depopulation of the excited states on the properties of the solvent used.

Spin-state switching in iron(II) complexes composed of ligands featuring moderate ligand-field strength-for example, 2,6-bi(1H-pyrazol-1-yl)pyridine (BPP)-is dependent on many factors. Herein, we show that spin-state switching in isomeric iron(II) complexes composed of BPP-based ligands-ethyl 2,6-bis(1H-pyrazol-1-yl)isonicotinate (BPP-COOEt, L1) and (2,6-di(1H-pyrazol-1-yl)pyridin-4-yl)methylacetate (BPP-CH2OCOMe, L2)-is dependent on the nature of the substituent at the BPP skeleton. Bi-stable spin-state switching-with a thermal hysteresis width (ΔT1/2) of 44 K and switching temperature (T1/2) = 298 K in the first cycle-is observed for complex 1·CH3CN composed of L1 and BF4- counter anions. Conversely, the solvent-free isomeric counterpart of 1·CH3CN-complex 2a, composed of L2 and BF4- counter anions-was trapped in the high-spin (HS) state. For one of the polymorphs of complex 2b·CH3CN-2b·CH3CN-Y, Y denotes yellow colour of the crystals-composed of L2 and ClO4- counter anions, a gradual and non-hysteretic SCO is observed with T1/2 = 234 K. Complexes 1·CH3CN and 2b·CH3CN-Y also underwent light-induced spin-state switching at 5 K due to the light-induced excited spin-state trapping (LIESST) effect. Structures of the low-spin (LS) and HS forms of complex 1·CH3CN revealed that spin-state switching goes hand-in-hand with pronounced distortion of the trans-N{pyridyl}-Fe-N{pyridyl} angle (ϕ), whereas such distortion is not observed for 2b·CH3CN-Y. This observation points that distortion is one of the factors making the spin-state switching of 1·CH3CN hysteretic in the solid state. The observation of bi-stable spin-state switching with T1/2 centred at room temperature for 1·CH3CN indicates that technologically relevant spin-state switching profiles based on mononuclear iron(II) complexes can be obtained.

Abstract Novel hydrogen bond liquid crystal (HBLC) complexes are prepared from the combination of non-mesogenic (α, ω-dicarboxylic acid) 2, 2-Dimethylsuccinic acid (DMSA) and liquid crystalline 4-n-alkyloxybenzoic acids (nOBA, n = 7 to 12). Mesogenic behavior of all complexes is analyzed by polarized optical microscope (POM) along with their thermal properties using differential scanning calorimeter (DSC). The microstructure of DMSA + 11OBA HBLC complex is observed by Field emission-scanning electron microscope (FE-SEM). The molecular geometry of DMSA + 7OBA HBLC complex is optimized. Intermolecular H-bonding of complexes is evinced using experimental and theoretical Fourier transform infrared spectroscopy (FTIR). Natural bonding orbitals (NBO) study supported the occurrence of H-bonds. GRAPHICAL ABSTRACT

Microenvironments tailored by multifunctional secondary coordination sphere groups can enhance catalytic performance at primary metal active sites in natural systems. Here, we capture this biological concept in synthetic systems by developing a family of iron porphyrins decorated with imidazolium (im) pendants for the electrochemical CO 2 reduction reaction (CO 2 RR), which promotes multiple synergistic effects to enhance CO 2 RR and enables the disentangling of second-sphere contributions that stem from each type of interaction. Fe- ortho -im(H) , which poises imidazolium units featuring both positive charge and hydrogen-bond capabilities proximal to the active iron center, increases CO 2 binding affinity by 25-fold and CO 2 RR activity by 2,000-fold relative to the parent Fe tetraphenylporphyrin ( Fe-TPP ). Comparison with mono-functional analogs reveals that through-space charge effects have a greater impact on catalytic CO 2 RR performance compared to hydrogen bonding in this context.

The cathodic two‐electron (2e‐) oxygen reduction reaction (ORR) has garnered much attention for electrosynthesis of hydrogen peroxide (H2O2). The transition metal single‐atom catalysts (SACs) with tunable geometry structure and electron layout have displayed promising potential in this process. Notably, atomically dispersed Fe‐based electrocatalysts have been recognized as high‐activity yet poor‐selectivity catalysts in 2e‐ ORR due to the high binding energy with the intermediates to break the peroxy bond into H2O. In this Concept, we briefly review the Fe SAC in 2e‐ ORR for H2O2 production by introducing their fundamental mechanism, chemical process, experimental advancements, and practical applications. The issues encountered and corresponding suggestions are discussed. The customized and tailored isolated Fe motif could fulfill the high activity, selectivity and stability system for H2O2 synthesis.

Based on first principles density functional theory (DFT) methods, this study employed the Cambridge Serial Total Energy Package (CASTEP) module within Materials Studio (MS) software under the generalized gradient approximation to investigate the adsorption, diffusion behavior, and electronic properties of hydrogen atoms on α-Fe(110) and α-Fe(110)-Me (Mn, Cr, Ni, Mo) surfaces, including calculations of their adsorption energies and density of states (DOS). The results demonstrated that doping with alloy atoms Me increased the physical adsorption energy of H2 molecules on the surface. Specifically, Mo doping elevated the adsorption energy from −1.00825 eV to −0.70226 eV, with the largest relative change being 30.35%. After doping with Me, the chemical adsorption energy of two hydrogen atoms does not change significantly, among which doping with Cr results in a decrease in the chemical adsorption energy. Building on this, further analysis of the chemical adsorption of single atoms on the surface was conducted. By comparing the adsorption energy and the bond length between a hydrogen atom and iron/dopant metal atom, it was found that Mo doping has the greatest impact, increasing the bond length by 58.58%. Analysis of the DOS functions under different doping conditions validated the interaction between different alloy elements and H atoms. Simultaneously, simulations were carried out on the energy barrier crossed by H atoms diffusing into the metal interior. The results indicate that Ni doping facilitates the diffusion of H atoms, while Cr, Mn, and Mo hinder their diffusion, with Mo having the most significant effect, where its barrier is 21.88 times that of the undoped surface. This conclusion offers deep insights into the impact of different doping elements on hydrogen adsorption and diffusion, aiding in the design of materials resistant to hydrogen embrittlement.

Understanding the characteristics of nitric oxide (NO) adsorption on metal-loaded zeolites is a prerequisite for developing efficient catalysts for NO abatement reactions. In this study, we probed the effect of the hydrogen bond that exists between adsorbed NO and Brønsted acid sites (BAS) in various metal-loaded ZSM-5 zeolites (M-ZSM-5, wherein M = Fe, Co, Ni, Cu, Zn, Pd, Ag, and Au) by using density functional theory calculations. The presence of a hydrogen bond has altered the NO adsorption energies significantly; appreciable stabilization via hydrogen bonding is noted for NO complexes of Zn, Fe, and Co, and reasonable stabilization is obtained for Ni and Cu complexes, whereas an anomalous effect of a hydrogen bond is identified in Ag, Pd, and Au species. Moderate weakening of the N-O bond in all NO-adsorbed complexes primarily due to a hydrogen bond has been realized in terms of Mayer bond order and quantum theory of atoms in molecules topological analyses; N-O bond activation follows the order Ag < Pd < Au < Ni < Cu < Co < Fe < Zn. We obtained a good correlation between hydrogen bond distance and molecular electrostatic potential at the O atom (VO) of NO adsorbed on BAS-free M-ZSM-5; which suggests that VO can be considered as a key descriptor to infer the strength of a hydrogen bond between the adsorbed NO and M-ZSM-5 with BAS. Finally, the energy decomposition analysis in combination with natural orbitals for chemical valence has provided the qualitative aspects of electron back-donation from the metal to the antibonding molecular orbital of NO; this back-donation is quite impressive in hydrogen-bond-assisted NO adsorption. We expect that the findings of this study will open up the possibility of the design of BAS-containing metal-loaded zeolites for the catalytic mitigation of NO.

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Single-atom metal-anchored porphyrin-based metal-organic frameworks (MOFs) have shown excellent light absorption, catalytic sites, and high stability during photocatalytic reactions, while there are still challenges for facile assembly with quantum dots to enhance catalytic dynamics. Herein, a kind of Fe single atom-doped MOF material (Fe-MOF-525) was ball milled with CdS in a proper ratio through Fe-N4 and Fe-N-C bonding, which showed the enhanced photoinduced carrier separation ability. As a result, extended light absorption ranges of CdS/Fe-MOF-5252.3 induced the promotion of the photocatalytic hydrogen (H2) value (3638.6 μmol g-1 h-1), which was 7.2 and 2.3 times higher than those of Fe-MOF-525 and CdS. In this work, the facile synthetic technique, specific active sites, and enhanced catalytic dynamics in the composite highlight the future research on MOF-based heterojunctions and their potential photocatalysis applications..

The crystal structure and magnetic properties of two mononuclear iron(iii) Schiff base complexes, [FeL1(NCS)2] (1), HL1 = 2-[1-[[2-[(2-aminoethyl)amino]ethyl]imino]ethyl]phenol and [FeL2(N3)Cl] (2), HL2 = 2-(-1-(2-(2-aminoethylamino)ethylimino)ethyl)-4-methylphenol are reported. Each complex contains a Fe(iii) ion surrounded by a N3O Schiff base ligand and two NCS− ligands (in 1) or one N3− and one Cl− ligands (in 2). The magnetic properties can be well reproduced with zero field splittings in the high spin S = 5/2 Fe(iii) ions and weak intermolecular Fe–Fe interactions mediated by hydrogen bonds. This intermolecular antiferromagnetic interaction has been validated by using DFT calculations in complex 2. Moreover, the interaction energies of the H-bonded dimers in both complexes have been estimated using DFT calculations and characterized using a combination of QTAIM and NCI plot computational tools. Complexes 1 and 2 constitute two rare examples of Fe(iii) complexes with magnetic interactions through H-bonds.

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Graphitic carbon nitride has emerged as a promising material for high-performance membranes with both filtration and catalytic abilities. However, the scalable construction of carbon-nitride-based membranes is seriously restricted by the poor ability to tailor the structure and poor solvent solubility of bulk nanostructures. Herein, carbon nitride sol was prepared in high yield and used as a precursor to assemble photo-Fenton-like membranes. Intermolecular hydrogen-bond interactions between carbon nitride nanofibers were found to be vitally important for the repolymerization of hydrolyzed molecules into dense and solid membranes. Intercalated Fe-containing polyoxometalates (Fe-POMs) not only acted as molecular linkers to construct carbon nitride membranes but also provided new opportunities for the catalytic functionality. Benefiting from the hydrophobic nanocapillaries in 2D carbon nitride for ultralow water-carbon friction, self-assembled membranes effectively rejected pollutant molecules with high water permeation flux. The integration of carbon nitride photocatalysts with Fenton-like Fe-POMs contributed to the in situ degradation of retained pollutants. Thus, our work manifested a facile bottom-up strategy to construct photo-Fenton-like membranes with antifouling abilities for wastewater treatment.

Spin crossover (SCO) complexes, which exhibit changes in spin state in response to external stimuli, have applications in molecular electronics and are challenging materials for computational design. We curate a dataset of 95 Fe(II) SCO complexes (SCO-95) from the Cambridge Structural Database that have available low- and high-temperature crystal structures and, in most cases, confirmed experimental spin transition temperatures (T1/2). We study these complexes using density functional theory (DFT) with 30 functionals spanning across multiple rungs of "Jacob's ladder" to understand the effect of exchange-correlation functional on electronic and Gibbs free energies associated with spin crossover. We specifically assess the effect of varying the Hartree-Fock exchange fraction (aHF) in structures and properties within the B3LYP family of functionals. We identify three best-performing functionals, a modified version of B3LYP (aHF = 0.10), M06-L, and TPSSh, that accurately predict SCO behavior for the majority of the complexes. While M06-L performs well, MN15-L, a more recently developed Minnesota functional, fails to predict SCO behavior for all complexes, which could be the result of differences in datasets used for parametrization of M06-L and MN15-L and also the increased number of parameters for MN15-L. Contrary to observations from prior studies, double-hybrids with higher aHF values are found to strongly stabilize high-spin states and therefore exhibit poor performance in predicting SCO behavior. Computationally predicted T1/2 values are consistent among the three functionals but show limited correlation to experimentally reported T1/2 values. These failures are attributed to the lack of crystal packing effects and counter-anions in the DFT calculations that would be needed to account for phenomena such as hysteresis and two-step SCO behavior. The SCO-95 set thus presents opportunities for method development, both in terms of increasing model complexity and method fidelity.

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This work aims to evaluate, from a static and dynamic perspective, the performance of a polycarboxylic acid-based scale inhibitor in the presence of iron ions (FeIII). The static (jar test) and dynamic (tube blocking test) tests were performed according to NACE TM0197-2010 and NACE TM31105-2005 standards, respectively. The lowest inhibition concentration (LIC) was determined under flow conditions of oil wells. In addition, the influence of the concentration of FeIII ions on the precipitation process was also evaluated. The scale deposits were analyzed by X-ray diffraction (XRD), infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The results demonstrated that the scale inhibitor is chemically compatible and efficient with the selected brines, possessing a LIC of 30 mg L-1 in the absence of FeIII ions. In the presence of FeIII ions, the inhibitor proved to be inefficient and incompatible, and it was not possible to determine the LIC. The combined XRD, FTIR, and SEM analyses allowed us to identify the inhibitor’s mechanism of action as being one of complexation, poly(carboxylic acid)-Ca2+. Furthermore, analyses in the presence of FeIII ions demonstrated a significant change in the morphology of the incrustation of CaCO3 crystals. Additionally, it has been proven that FeIII ions significantly affect the performance of the inhibitor. Finally, the results indicated that in the absence of high concentrations of FeIII ions, the poly(carboxylic acid) scale inhibitors can be an option to mitigate operating costs resulting from the deposition of inorganic scale in oil wells.

Selective catalytic transformations play a crucial role in organic synthesis, with chemodivergent synthesis holding particular significance. Key reactions in this context involve the selective oxidations of alcohols, leading to either the formation of corresponding carbonyls or complete oxidation to carboxylic acids. The use of base metal iron in catalysis is noteworthy due to its abundance, cost-effectiveness, nontoxicity, and sustainability. As a result, research on iron-catalyzed alcohol oxidation holds considerable importance. A tridentate NNN ligand was employed to yield an air-stable iron complex (1), proving to be an efficient catalyst for the selective oxidation of primary alcohols to aldehydes using TBHP as the oxidant without the addition of any solvent. The same iron complex demonstrated high efficiency in the selective oxidation of primary alcohols to carboxylic acids in a deep eutectic solvent (DES). Notably, the DES environment allowed achieving ppm-level catalyst loading (TON: 100,000 and TOF: 100,000 h-1). This is an excellent example of reaction media-induced chemodivergent oxidation of primary alcohols to aldehydes and carboxylic acids. A wide range of activated and unactivated primary alcohols was oxidized to the corresponding aldehydes and carboxylic acids selectively. Control experiments suggest a plausible homogeneous catalytic reaction pathway involving a radical mechanism.

Carboxylic acids, a bench-stable, readily available, and structurally diverse class of compounds, represent ideal starting materials for organic synthesis. In this article, we highlight an iron-catalyzed, decarboxylative, C(sp 3 )–O bond-forming reaction that takes place under mild, photocatalytic, base-free conditions using 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) derivatives as oxygenation reagents. The reaction is enabled by the ability of iron complexes to generate carbon-centered radicals directly from carboxylic acids through a sequence involving a photoinduced carboxylate-to-iron charge transfer, homolysis, and loss of carbon dioxide. The developed transformation displays exquisite substrate tolerance and was applied to various bioactive molecules. We performed an extensive mechanistic investigation through kinetic studies; electrochemistry, EPR, UV/Vis, and HRMS analyses; and DFT calculations. Those studies suggest that TEMPO plays three different roles in the reaction: it acts as an oxygenation reagent, serves as an oxidant to regenerate the Fe catalyst, and functions as an internal base for carboxylic acid deprotonation. The resulting TEMPO adducts are versatile synthons that can be subsequently utilized in C–C and C–heteroatom bond-forming reactions employing commercially available organophotocatalysts and nucleophilic reagents. 1 Introduction 2 Background on the LMCT Reactivity of Iron Complexes 3 Direct Iron-Photocatalyzed Decarboxylative Oxygenation: Reaction Concept 4 Substrate Scope Assessment of Decarboxylative Oxygenation 5 Mechanistic Considerations 6 Conclusion

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A mononuclear iron(II) complex, [(TpPh2)FeII(OTf)(CH3CN)] (1) (TpPh2 = hydrotris(3,5-diphenylpyrazol-1-yl)borate, OTf = triflate) has been isolated and its efficiency toward the aliphatic CC bond cleavage reaction of 1,2-diols with dioxygen has been investigated. Separate reactions between 1 and different 1,2-diolates form the corresponding iron(II)-diolate complexes in solution. While the iron(II) complex of the tetradentate TPA (tris(2-pyridylmethyl)amine) ligand is not efficient in affecting the CC cleavage of 1,2-diol with dioxygen, complex 1 displays catalytic activity to afford carboxylic acid and aldehyde. Isotope labeling studies with 18O2 reveal that one oxygen atom from dioxygen is incorporated into the carboxylic acid product. The oxygenative CC cleavage reactions occur on the 1,2-diols containing at least one α-H atom. The kinetic isotope effect value of 5.7 supports the abstraction of an α-H by an iron(III)-superoxo species to propagate the CC cleavage reactions. The oxidative cleavage of 1,2-diolates by the iron(II) complex mimics the reaction catalyzed by the nonheme diiron enzyme, myo-inositol oxygenase.

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Fe(III) and carboxylic acids are common compositions in atmospheric microdroplet systems like clouds, fogs, and aerosols. Although photochemical processes of Fe(III)-carboxylate complexes have been extensively studied in bulk aqueous solution, relevant information on the dynamic microdroplet system, which may be largely different from the bulk phase, is rare. With the help of the custom-made ultrasonic-based dynamic microdroplet photochemical system, this study examines the photochemical process of Fe(III)-citric acid complexes in microdroplets for the first time. We find that when the degradation extent of citric acid is similar between the microdroplet system and the bulk solution, the significantly lower Fe(II) ratio is present in microdroplet samples due to the rapider reoxidation of photogenerated Fe(II). However, by replacing citric acid with benzoic acid, no much difference in the Fe(II) ratio between microdroplets and bulk solution is observed, which indicates distinct reoxidation pathways of Fe(II). Moreover, the presence of •OH scavenger, namely, methanol, greatly accelerates the reoxidation of photogenerated Fe(II) in both citric acid and benzoic acid situations. Further experiments reveal that the high availability of O2 and the citric acid- or methanol-derived carbon-centered radicals are responsible for the rapider reoxidation of Fe(II) in iron-citric acid microdroplets by prolonging the length of HO2•- and H2O2-involved radical reaction chains. The results in this study may provide a new understanding about iron-citric acid photochemistry in atmospheric liquid particles, which can further influence the photoactivity of particles and the formation of secondary organic aerosols.

A practical and general iron-catalyzed domino decarboxylation-oxidation of α,β-unsaturated carboxylic acids enabling aldehyde C-H methylation for the synthesis of methyl ketones has been developed. This mild, operationally simple method uses ambient air as the sole oxidant and tolerates sensitive functional groups for the late-stage functionalization of complex natural-product-derived and polyfunctionalized molecules.

Iron and organic carbon (OC) biogeochemical cycling is highly correlated, and dissolved organic matter (DOM), a highly reactive component of soil and water environments, is the main OC source. However, the micro-mechanism of the molecular fractionation of DOM, the spatial OC distribution on iron (oxyhydr)oxides, and how these factors further affect their redox properties remain to be fully understood. Therefore, this study investigated the DOM adsorption properties of iron (oxyhydr)oxides with different crystallinities at the molecular level through the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and transmission electron microscopy/electron energy loss spectroscopy (TEM-EELS) analyses of the liquid-solid phases. Owing to the limited number of adsorption sites, OC sequestration on goethite and hematite surfaces generally followed an "onion" model, in the order of preference of aromatic, aliphatic, and carboxylic acid-rich compounds. Combined with dielectric electrochemical tests and charge differential density calculations, the results revealed that the complexation effect produced by iron ions increased the electron-accepting capacity (EAC) of the DOM remaining in the aqueous solution. In contrast, molecular selective adsorption and oxidative polymerization significantly enhanced the EAC of DOM adsorbed on the surface fraction of iron (oxyhydr)oxides. These findings help elucidate the mechanism of OC sequestration by iron (oxyhydr)oxides. The increased EAC may affect various biogeochemical processes, such as methane production and microbial Fe(III) reduction, facilitating the prediction of OC cycling in natural environments.

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Abstract C42H32F2Fe2O4P2Te2, monoclinic, P21 (no. 4), a = 10.8243(9) Å, b = 16.7702(15) Å, c = 12.1105(12) Å, β = 114.079(5) ° ^{\circ} , , V = 2007.1(3) Å3, Z = 2, R gt (F) = 0.0472, wR ref (F2) = 0.1188, T = 293(2) K.

Abstract C13H6Fe2O6S2, monoclinic, P21/c (no. 14), a = 10.0181(3) Å, b = 6.4719(2) Å, c = 24.3922(6) Å, β = 94.630(1)°, V = 1576.34(8) Å3, Z = 4, Rgt(F) = 0.0245, wRref(F2) = 0.0566, T = 150(2) K.

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Abstract C47H37Fe2NO4P2Se2, monoclinic, P21/n (no. 14), a = 12.8144(11) Å, b = 17.9714(15) Å, c = 19.1077(17) Å, β = 104.329(4)°, V = 4263.5(6) Å3, Z = 4, R gt (F) = 0.0420, wR ref (F 2) = 0.0968, T = 298(2) K.

Abstract C48H39Fe2NO4P2S2, orthorhombic, P21 (no. 4), a = 11.4073(11) Å, b = 16.9013(14) Å, c = 11.8261(12) Å, α = 90°, β = 108.297(4)°, γ = 90°, V = 2164.8(4) Å3, Z = 2, R gt(F) = 0.0355, wR ref(F 2) = 0.0740, T = 298(2) K.

The peak-loading shift function of sodium-ion batteries in large-grid energy store station poses a giant challenge on the account of poor rate performance of cathodes. NASICON type Na3V2(PO4)3 with a stable three-dimensional framework and fast ion diffusion channels has been regarded as one of the potential candidates and extensively studied. Nevertheless, a multilevel integrated tactic to boost the performance of Na3V2(PO4)3 in terms of crystal structure modulation, coated carbon graphitization regulation, and particle morphology design is rarely reported and deserves much attention. In this study, organic ferric was used to prepare Fe-doped Na3V2(PO4)3@C cathode on the account of low cost, environmental friendliness, and catalytic function of Fe on carbon graphitization. The density functional theory calculation depicts that the most stable site for Fe atom is the V site and moderate replacement of Fe at V position would reduce the band gap energy from 2.19 by 0.43 eV and improve the electron transfer, which is crucial for the intrinsic poor conductivity of Na3V2(PO4)3. The experimental results show that Fe element can be introduced into the bulk structure successfully, modulating relevant structural parameters. In addition, the coated carbon layer graphitization degree is also regulated due to the catalysis function of Fe. And, the decomposition of organic ferric would infuse the formation of porous structure, which can promote electrolyte permeation and shorten the electron/ion diffusion. Finally, the optimized Na3V1.85Fe0.15(PO4)3@C could possess a high capacity of 103.69 mA h g-1 and retain 91.45% after 1200 cycles at 1.0C as well as 94.45 mA h g-1 at 20C. In addition, the excellent performance is comprehensively elucidated via ex situ X-ray diffraction and pseudocapacitance characterization. The multifunction contribution of Fe-doping may provide new clue for designing porous electrode materials and a new sight into Fe-doped carbon-coated material.

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