Search

In this work, we report the synthesis of a room-temperature-stable electride (RoSE) reagent, namely K+(LiHMDS)e− (1) (HMDS: 1,1,1,3,3,3-hexamethyldisilazide), from accessible starting materials (potassium metal and LiHMDS) via mechanochemical ball milling at 20 mmol scale. Despite its amorphous nature, the presence of anionic electrons in 1, key diagnostic criteria for an electride, was confirmed by both experimental and computational studies. Therefore, by definition, 1 is an electride. Utilizing its anionic electrons, electride reagent 1 exhibited a versatile reactivity profile that includes (1) mediation of C–H activation and C–C coupling of benzene and pyridine and (2) mediation of solvent-free Birch reduction. This work proves the concept of facile mechanochemical synthesis of a room-temperature-stable electride, and it introduces electride 1 to the synthetic chemistry community as a versatile reagent.

Formation of multi-carbon (C2+) products by electrochemical reduction of CO2 using two porous Cu(ii)-based materials (HKUST-1 and CuMOP, MOP = metal–organic polyhedra) under electrochemical conditions in the presence of TNCQ.

An oxindolimine-copper(ii) complex with antitumor properties was immobilized in a silica matrix, and verified to be more active and selective due the formation of a dinuclear species, unveiled by continuous wave and pulsed EPR spectroscopy.

A small but growing number of molecular compounds have been isolated featuring divalent lanthanides with 4f

The presence of active sites in metal-organic framework (MOF) materials can control and affect their performance significantly in adsorption and catalysis. However, revealing the interactions between the substrate and active sites in MOFs at atomic precision remains a challenging task. Here, we report the direct observation of binding of NH3 in a series of UiO-66 materials containing atomically dispersed defects and open Cu(I) and Cu(II) sites. While all MOFs in this series exhibit similar surface areas (1111-1135 m2 g-1), decoration of the-OH site in UiO-66-defect with Cu(II) results in a 43% enhancement of the isothermal uptake of NH3 at 273 K and 1.0 bar from 11.8 in UiO-66-defect to 16.9 mmol g-1 in UiO-66-CuII. A 100% enhancement of dynamic adsorption of NH3 at a concentration level of 630 ppm from 2.07 mmol g-1 in UiO-66-defect to 4.15 mmol g-1 in UiO-66-CuII at 298 K is observed. In situ neutron powder diffraction, inelastic neutron scattering, and electron paramagnetic resonance, solid-state nuclear magnetic resonance, and infrared spectroscopies, coupled with modeling reveal that the enhanced NH3 uptake in UiO-66-CuII originates from a {Cu(II)···NH3} interaction, with a reversible change in geometry at Cu(II) from near-linear to trigonal coordination. This work represents the first example of structural elucidation of NH3 binding in MOFs containing open metal sites and will inform the design of new efficient MOF sorbents by targeted control of active sites for NH3 capture and storage.

[FeL2]X2·2H2O (L = 2,6-bis{5-methyl-1H-pyrazol-3-yl}pyridine; X− = BF4− or ClO4−) are readily dehydrated upon mild heating. Anhydrous [FeL2][BF4]2 exhibits an abrupt spin-transition at T1/2 = 205 K, with a 65 K thermal hysteresis loop which narrows upon repeated scanning. The isomorphous ClO4− salt remains high-spin on cooling, however, which is investigated further in this study. Unlike the iron complex, [ZnL2][ClO4]2·2H2O undergoes single-crystal-to-single-crystal dehydration; the tetragonal anhydrous crystals transform to a new triclinic phase upon cooling. The phase change is apparently sluggish and transition temperatures between 268 K and

Manganese (II) xanthate complexes of the form [Mn(S2COR)2(TMEDA)], where TMEDA = tetramethylethylenediamine and R = methyl (1), ethyl (2), n-propyl (3), n-butyl (4), n-pentyl (5), n-hexyl (6) and n-octyl (7), have been synthesised and structures elucidated using single crystal X-ray diffraction. Complexes 1 to 7 were used as molecular precursors to synthesise manganese sulfide (MnS). Olelyamine (OLA) capped nanocrystals have been produced via hot injection, whilst the doctor blading followed by thermolysis yielded thick films. Free-standing polycrystalline powders of MnS are produced by direct thermolysis of precursor powders. All thermolysis techniques produced cubic MnS as confirmed by powder X-ray diffraction, scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy and Raman spectroscopy. Magnetic measurements reveal that the α-MnS nanocrystals exhibit ferromagnetic behaviour with a large coercive field strength (e.g., 0.723 kOe for 6.8 nm nanocrystals).

The production of conjugated C4-C5 dienes from biomass can enable the sustainable synthesis of many important polymers and liquid fuels. Here, we report the first example of bimetallic (Nb, Al)-atomically doped mesoporous silica, denoted as AlNb-MCM-41, which affords quantitative conversion of 2-methyltetrahydrofuran (2-MTHF) to pentadienes with a high selectivity of 91 %. The incorporation of Al

Increasing levels of air pollution are driving the need for the development new processes that take ‘waste-to-chemicals’. Herein we report the capture and conversion under ambient conditions of a major air pollutant, NO2, using a robust metal-organic framework (MOF) material, Zr-bptc (H4bptc = 3, 3’, 5, 5’-biphenyltetracarboxylic acid), comprising of {Zr6(μ3-O)4(μ3-OH)4(COO)12} clusters linked by 4-connected bptc4− ligands in a ftw topology. At 298 K, Zr-bptc shows exceptional stability and adsorption of NO2 at both low (4.9 mmol g-1 at 10 mbar) and high pressures (13.8 mmol g-1 at 1.0 bar) as measured by isotherm experiments. Dynamic breakthrough experiments have confirmed the selective retention of NO2 by Zr-bptc at low concentrations under both dry and wet conditions. The immobilised NO2 can be readily transformed to valuable nitro compounds relevant to construction, agrochemical and pharmaceutical industries. In situ crystallographic and spectroscopic studies reveal strong binding interactions of NO2 to the {Zr6(μ3-O)4(μ3-OH)4(COO)12} cluster node. This study paves a circular pathway to enable the integration of nitrogen-based air pollutants into the production of fine chemicals.

Selective oxidation of benzylic C−H compounds to ketones is important for the production of a wide range of fine chemicals, and is often achieved using toxic or precious metal catalysts. Herein, we report the efficient oxidation of benzylic C−H groups in a broad range of substrates under mild conditions over a robust metal–organic framework material, MFM‐170, incorporating redox‐active [Cu2 II(O2CR)4] paddlewheel nodes. A comprehensive investigation employing electron paramagnetic resonance (EPR) spectroscopy and synchrotron X‐ray diffraction has identified the critical role of the paddlewheel moiety in activating the oxidant tBuOOH (tert‐butyl hydroperoxide) via partial reduction to [CuIICuI(O2CR)4] species., The oxidation of benzylic C−H groups in a broad range of substrates under mild conditions has been achieved using a robust metal–organic framework, MFM‐170, incorporating redox‐active [Cu2 II(O2CR)4] paddlewheel nodes. EPR spectroscopy and synchrotron X‐ray diffraction have identified the critical role of the paddlewheel moiety in activating the oxidant tBuOOH (tert‐butyl hydroperoxide) via partial reduction to [CuIICuI(O2CR)4] species.

Summary A fundamental part of characterizing any metal complex is understanding its electronic ground state, for which magnetometry provides key insight. Most uranium(IV) complexes exhibit low-temperature magnetic moments tending to zero, consistent with a non-degenerate spin-orbit ground state. However, there is a growing number of uranium(IV) complexes with low-temperature magnetic moments ≥1 μB, suggesting a degenerate ground state, but the electronic structure implications and origins have been unclear. We report uranium(IV)-oxo and -imido complexes with low-temperature magnetic moments (ca. 1.5–1.6 μB) and show that they exhibit near-doubly degenerate spin-orbit ground states. We determine that this results from the strong point-charge-like donor properties of oxo and imido anions generating pseudosymmetric electronic structures and that traditional crystal field arguments are useful for understanding electronic structure and magnetic properties of uranium(IV). This suggests that a significant number of uranium(IV) complexes might benefit from a close re-evaluation of the nature of their spin-orbit ground states.

Here we explore the electronic structure of the diiron complex [(dppf)Fe(CO)3]0/+ [10/+; dppf = 1,1'-bis(diphenylphosphino)ferrocene] in two oxidation states by an advanced multitechnique experimental approach. A combination of magnetic circular dichroism, X-ray absorption and emission, high-frequency electron paramagnetic resonance (EPR), and Mossbauer spectroscopies is used to establish that oxidation of 10 occurs on the carbonyl iron ion, resulting in a low-spin iron(I) ion. It is shown that an unequivocal result is obtained by combining several methods. Compound 1+ displays slow spin dynamics, which is used here to study its geometric structure by means of pulsed EPR methods. Surprisingly, these data show an association of the tetrakis[3,5-bis(trifluoromethylphenyl)]borate counterion with 1+.

Optimising the balance between propene selectivity, propene/ethene ratio and catalytic stability and unravelling the explicit mechanism on formation of the first carbon–carbon bond are challenging goals of great importance in state-of-the-art methanol-to-olefin (MTO) research. We report a strategy to finely control the nature of active sites within the pores of commercial MFI-zeolites by incorporating tantalum(V) and aluminium(III) centres into the framework. The resultant TaAlS-1 zeolite exhibits simultaneously remarkable propene selectivity (51%), propene/ethene ratio (8.3) and catalytic stability (>50 h) at full methanol conversion. In situ synchrotron X-ray powder diffraction, X-ray absorption spectroscopy and inelastic neutron scattering coupled with DFT calculations reveal that the first carbon–carbon bond is formed between an activated methanol molecule and a trimethyloxonium intermediate. The unprecedented cooperativity between tantalum(V) and Brønsted acid sites creates an optimal microenvironment for efficient conversion of methanol and thus greatly promotes the application of zeolites in the sustainable manufacturing of light olefins., We thank EPSRC (EP/P011632/1), the Royal Society, National Natural Science Foundation of China (21733011, 21890761, 21673076), and the University of Manchester for funding. We thank EPSRC for funding and the EPSRC National Service for EPR Spectroscopy at Manchester. A.M.S. is supported by a Royal Society Newton International Fellowship. We are grateful to the STFC/ISIS Facility, Oak Ridge National Laboratory (ORNL) and Diamond Light Source (DLS) for access to the beamlines TOSCA/MAPS, VISION and I11/I20, respectively. We acknowledge Dr. L. Keenan for help at I20 beamline (SP23594-1). UK Catalysis Hub is kindly thanked for resources and support provided via our membership of the UK Catalysis Hub Consortium and funded by EPSRC grant: EP/R026939/1, EP/R026815/1, EP/R026645/1, EP/R027129/1 or EP/M013219/1 (biocatalysis). We acknowledge the support of The University of Manchester’s Dalton Cumbrian Facility (DCF), a partner in the National Nuclear User Facility, the EPSRC UK National Ion Beam Centre and the Henry Royce Institute. We recognise Dr. R. Edge and Dr. K. Warren for their assistance during the 60Co γ-irradiation processes. We thank Prof. A. Jentys from the Technical University of Munich for the measurement of the INS spectrum of iso-butene. We thank C. Webb, E. Enston and G. Smith for help with GC–MS; Dr. L. Hughes for help with SEM and EDX; M. Kibble for help at TOSCA/MAPS beamlines. Computing resources (time on the SCARF compute cluster for some of the CASTEP calculations) was provided by STFC’s e-Science facility. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by ORNL. The computing resources at ORNL were made available through the VirtuES and the ICE-MAN projects, funded by Laboratory Directed Research and Development programme and Compute and Data Environment for Science (CADES)

Electroactive metal-organic frameworks (MOFs) are an attractive class of materials owing to their multifunctional 3-dimensional structures, the properties of which can be modulated by changing the redox states of the components. In order to realise both fundamental and applied goals for these materials, a deeper understanding of the structure-function relationships that govern the charge transfer mechanisms is required. Chemical or electrochemical reduction of the framework [Zn(BPPFTzTz)(tdc)]·2DMF, hereafter denoted ZnFTzTz (where BPPFTzTz = 2,5-bis(3-fluoro-4-(pyridin-4-yl)phenyl)thiazolo[5,4-d]thiazole), generates mixed-valence states with optical signatures indicative of through-space intervalence charge transfer (IVCT) between the cofacially stacked ligands. Fluorination of the TzTz ligands influences the IVCT band parameters relative to the unsubstituted parent system, as revealed through Marcus-Hush theory analysis and single crystal UV-Vis spectroscopy. Using a combined experimental, theoretical and density functional theory (DFT) analysis, important insights into the effects of structural modifications, such as ligand substitution, on the degree of electronic coupling and rate of electron transfer have been obtained.

Self-assembly and characterisation of a supramolecular trigonal bipyramidal iron cage containing an [FeIII(μ2-F)6(FeII)3]3+ star motif at its core is reported. The complex can be formed in a one step reaction using an heterotopic ligand that supports site-specific incorporation of iron in three distinct electronic configurations: low-spin FeII, high-spin FeII and high-spin FeIII, with iron(II) tetrafluoroborate as the source of the bridging fluorides. Formation of a μ2-F bridged mixed-valence FeII-FeIII star is unprecedented. The peripheral high-spin FeII centres of the mixed-valence tetranuclear star incorporated in the iron cage are highly anisotropic and engage in F-mediated antiferromagnetic exchange with the central FeIII ion.

In situ growth of the metal–organic framework material MFM-300(Fe) on an ultra-thin sheet of graphitic carbon nitride (g-C3N4) has been achieved via exfoliation of bulk carbon nitride using supercritical CO2. The resultant hybrid structure, CNNS/MFM-300(Fe), comprising carbon nitride nanosheets (CNNS) and MFM-300(Fe), shows excellent performance towards photocatalytic aerobic oxidation of benzylic C–H groups at room temperature under visible light. The catalytic activity is significantly improved compared to the parent g-C3N4, MFM-300(Fe) or physical mixtures of both. This facile strategy for preparing heterojunction photocatalysts demonstrates a green pathway for the efficient and economic oxidation of benzylic carbons to produce fine chemicals., In situ growth of the MFM-300(Fe) on an ultra-thin sheet of graphitic carbon nitride, formed by exfoliation using supercritical CO2, is reported. The resultant composite CNNS/MFM-300(Fe) shows excellent performance in photocatalytic aerobic oxidation of benzylic C–H groups.

Understanding the structural and chemical changes that reactive metal-organic frameworks (MOFs) undergo is crucial for the development of new efficient catalysts for electrochemical reduction of CO

International audience; A new nitronyl-nitroxide ligand (H2L) featuring alcoholic and phenolic groups has been synthesised starting from 2-hydroxy-3-(hydroxymethyl)-5-methylbenzaldehyde (A). Using this ligand, three 2p–4 f binuclear complexes have been obtained and crystallographically characterized: [Ln2(HL)2(hfac)4], (Ln=Gd 1, Tb 2, Dy 3). Apart from the desired compounds, two by-products have been isolated as a molecular alloy containing an intermediate bearing hydroxylamino and N-oxide groups, i. e. (1-hydroxy-2-(2-hydroxy-3-(hydroxymethyl)-5-methylphenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole 3-oxide, B, and the imino-nitroxide derivative, C. This system was characterized by single crystal X-ray diffraction, UV-VIS and EPR spectroscopy. During the synthesis of compounds 1–3, two other complexes have been obtained and characterized: [Ln(C)(hfac)3] (4, Ln=Tb) and [Ln2(A−H)2(hfac)4] (5, Ln=Tb), where (A−H) results from the deprotonation of the phenolic group in A. The synthetic procedure was optimized in order to obtain pure 1–3 complexes. The cryomagnetic properties of compounds 1–3 have been investigated. Continuous-wave (CW) electron paramagnetic resonance (EPR) measurements were carried out at X- and Q-band for compound 1. Time-dependent experiments were performed at three magnetic fields. Phase memory times, Tm, were found to be about 1000 ns at 6 K.

A series of heterometallic [TiIV7MIII] rings are reported which contain a single paramagnetic metal centre, either FeIII or CrIII. The structures contain an octagon of metals bridged by oxides within the ring and pivalate ligands outside the ring. The structures encapsulate a single cation, either a secondary ammonium cation or a cesium. Multi-frequency EPR spectroscopy was used to measure the zero-field splitting parameters for the paramagnetic metal sites. The FeIII sites have rhombic anisotropy, with D around − 0.18 cm−1 and λ (= D/E) approximately 0.25. The CrIII have a more axial anisotropy, with D around − 0.5 cm−1 and λ around 0.05. Attempts to find a magneto-structural correlation are vitiated by the difficulty of refining the challenging crystal structures.

Four 3d-4f hetero-polymetallic complexes [Fe2Ln2((OCH2)3CR)2(O2CtBu)6(H2O)4] (where Ln = La (1 and 2) and Gd (3 and 4); and R = Me (1 and 3) and Et (2 and 4)) are synthesized and analyzed using elemental analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, and SQUID magnetometry. Crystal structures are obtained for both methyl derivatives and show that the complexes are isostructural and adopt a defective dicubane topology. The four heavy metals are connected with two alkoxide bridges. These four precursors are used as single-source precursors to prepare rare-earth orthoferrite pervoskites of the form LnFeO3. Thermal decomposition in a ceramic boat in a tube furnace gives orthorhombic LnFeO3 powders using optimized temperatures and decomposition times: LaFeO3 formed at 650 °C over 30 min, whereas GdFeO3 formed at 750 °C over 18 h. These materials are structurally characterized using powder X-ray diffraction, Raman spectroscopy, scanning electron microscopy, energy-dispersive X-ray map spectroscopy, and SQUID magnetometry. EDX spectroscopy mapping reveals a homogeneous spatial distribution of elements for all four materials consistent with LnFeO3. Magnetic measurements on complexes 1-4 confirm the presence of weak antiferromagnetic coupling between the central Fe(III) ions of the clusters and negligible ferromagnetic interaction with peripheral Gd(III) ions in 3 and 4. Zero-field-cooled and field-cooled measurements of magnetization of LaFeO3 and GdFeO3 in the solid-state suggest that both materials are ferromagnetic, and both materials show open magnetic hysteresis loops at 5 and 300 K, with Msat higher than previously reported for these nanomaterials. We conclude that this is a new and facile low temperature route to these important magnetic materials that is potentially universal, limited only by what metals can be programmed into the precursor complexes.

Stabilised amorphous selenium (a-Se) is currently used in the majority of direct conversion mammographic X-ray imaging detectors due to its X-ray photoconductivity and its ability to be uniformly deposited over large area TFT substrates by conventional vacuum deposition. We report experimental results on photocurrent spectroscopy (frequency-resolved spectroscopy (FRS) and single-time transients), on vacuum-deposited a-Se films. We show that all measured photocurrents depend critically on the relative time spent by the material in the light and in the dark. We identify that the observed pronounced variation in optical response depends on the density of trapped (optically injected) charge within 200 nm of the surface and show that it is the ratio of dark and light exposure time that controls the density of such charge. Our data confirm that the localised charge radically influences the photocurrent transient shape due to the effective screening of the applied field within 200 nm of the surface. The field modification occurs over the optical extinction depth and changes both the photogeneration process and the drift of carriers. Many aspects of our data carry the signature of known properties of valence alternation pair (VAP) defects, which control many properties of a-Se. Modelling in the time domain shows that light generation of VAPs followed by optically triggered VAP defect conversion can lead to near-surface charge imbalance, demonstrating that VAP defects can account for the unusual optical response. The stabilised a-Se films were deposited above the glass transition temperature of the alloy with composition a-Se:0.3% As doped with ppm Cl. Electron paramagnetic resonance measurements at temperatures down to 5 K did not detect any spin active defects, even under photoexcitation above band gap.

The molecular design of spin-crossover complexes relies on controlling the spin state of a transition metal ion by proper chemical modifications of the ligands. Herein, the first N,N'-disubstituted 2,6-bis(pyrazol-3-yl)pyridines (3-bpp) are reported 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.

A homoleptic gadolinium(III) complex with the smallest helicene-type ligand, 1,10-phenanthroline-N,N'-dioxide (phendo) [Gd(phendo)4](NO3)3·xMeOH (phendo = 1,10-phenanthroline-N,N'-dioxide, MeOH = methanol), shows slow relaxation of the magnetization characteristic for Single Ion Magnets (SIM), despite negligible magnetic anisotropy, confirmed by ab initio calculations. Solid state dilution magnetic and EPR studies reveal that the magnetization dynamics of the [Gd(phendo)4]3+ cation is controlled mainly by a Raman process. Pulsed EPR experiments demonstrate long phase memory times (up to 2.7 μs at 5 K), enabling the detection of Rabi oscillations at 20 K, which confirms coherent control of its spin state. ispartof: JOURNAL OF PHYSICAL CHEMISTRY LETTERS vol:11 issue:4 pages:1508-1515 ispartof: location:United States status: published

Gaining a fundamental understanding of charge transfer mechanisms in three-dimensional Metal–Organic Frameworks (MOFs) is crucial to the development of electroactive and conductive porous materials. These materials have potential in applications in porous conductors, electrocatalysts and energy storage devices; however the structure–property relationships pertaining to charge transfer and its quantification are relatively poorly understood. Here, the cofacial Cd(II)-based MOF [Cd(BPPTzTz)(tdc)]·2DMF (where BPPTzTz = 2,5-bis(4-(pyridin-4-yl)phenyl)thiazolo[5,4-d]thiazole, tdc2− = 2,5-thiophene dicarboxylate) exhibits Intervalence Charge Transfer (IVCT) within its three-dimensional structure by virtue of the close, cofacial stacking of its redox-active BPPTzTz ligands. The mixed-valence and IVCT properties are characterised using a combined electrochemical, spectroelectrochemical and computational approach. Single crystal electronic absorption spectroscopy was employed to obtain the solid-state extinction coefficient, enabling the application of Marcus–Hush theory. The electronic coupling constant, Hab, of 145 cm−1 was consistent with the localised mixed-valence properties of both this framework and analogous systems that use alternative methods to obtain the Hab parameter. This work demonstrates the first report of the successful characterisation of IVCT in a MOF material using single crystal electronic absorption spectroscopy and serves as an attractive alternative to more complex methods due to its simplicity and applicability.

Propeller-like lanthanide complexes with suitable chiral ligand scaffolds are highly desired as they combine chirality with possible magnetic bistability. However, the library of relevant chiral lanthanide-based molecules is quite limited. Herein we present the preparation, structures, magnetic behavior as well as EPR studies of a series of propeller-shaped lanthanide Single Ion Magnets (SIMs). Coordination of the smallest helicene-type molecule 1,10-phenanthroline-N,N′-dioxide (phendo) to LnIII ions results in the formation of homoleptic complexes [LnIII(phendo)4](NO3)3·xMeOH (Ln = Gd, Er, Yb) Gd, Er and Yb, where four phendos encircle the metal center equatorially in a four-bladed propeller fashion. The magnetization dynamics in these systems is studied by magnetic measurements and EPR spectroscopy for non-diluted as well as solid state dilutions of Er and Yb in a diamagnetic [YIII(phendo)4](NO3)3·xMeOH (Y) matrix. Careful analysis of the slow magnetic relaxation in the diluted samples can be described by a combination of Raman and Orbach relaxation mechanisms. The most important finding concerns the identical power law τ ≈ T−3 describing the anomalous Raman relaxation for all three reported compounds diluted in the Y matrix. This identical power law strongly suggests that the exponent of the Raman relaxation process in the series of solid-state diluted isostructural compounds is practically independent of the metal ion (as long as the molar mass changes are negligible) and highlights a possible experimental strategy towards reliable Raman relaxation determination.

The interaction between α-synuclein (αSyn) and Cu2+ has been suggested to be closely linked to brain copper homeostasis. Disruption of copper levels could induce misfolding and aggregation of αSyn, and thus contribute to the progression of Parkinson's disease (PD). Understanding the molecular mechanism of αSyn-Cu2+ interaction is important but there still exist controversies in Cu2+ coordination geometry with αSyn. Herein, we find that the pathological H50Q mutation has no impact on the kinetics of Cu2+ binding to the high-affinity site of wild type αSyn (WT-αSyn), indicating the non-involvement of His50 in high-affinity Cu2+ binding to WT-αSyn. In contrast, the physiological N-terminally acetylated αSyn (NAc-αSyn) displays several orders of magnitude weaker Cu2+ binding affinity than WT-αSyn. Cu2+ coordination mode to NAc-αSyn has also been proposed based on EPR spectrum. In addition, we find that Cu2+ coordinated WT-αSyn is reduction-active in the presence of GSH, but essentially inactive towards ascorbate. Our work provides new insights into αSyn-Cu2+ interaction, which may help understand the multifaceted normal functions of αSyn as well as pathological consequences of αSyn aggregation.