Dimeric Copper Research Articles

Mechanochemical oxidative complexation of copper(I) chloride with acetic acid, benzoic acid, their chloro derivatives and l-histidine affording anhydrous copper(II) complexes

This work reports solvent-free synthesis of copper(II)-carboxylates by grinding the reactants in solid state (the mechanochemical method). Here we used copper(I) salt to synthesize copper(II) complexes to demonstrate the potential of oxidative synthesis of the mechanochemical technique. The complexes were synthesized by grinding copper(I) chloride with a carboxylic acid together in 1:2 molar ratio in mortar and pestle. The carboxylic acids used were acetic acid, benzoic acid, 2-chloroacetic acid, 2-chlorobenzoic acid and l-histidine. The oxidative complexation occurred in the solid state producing anhydrous dimeric copper(II)-carboxylates (except that of l-histidine) in quantitative yield (>96 %) having 1:2 metal to ligand ratio. The first evidence to oxidation of copper(I) to copper(II) ion was a change in color (pale to greenish blue) and a change in magnetic susceptibility from diamagnetic to paramagnetic value. The complexes were also characterized by elemental analysis, electronic absorption spectroscopy, FT-IR spectra, mass spectrometry, powder X-ray diffraction and thermal analysis. The electronic absorption, magnetic susceptibility, ESR and X-ray diffraction data supported a distorted square-planer geometry. This study provided for a distinct test in the form of magnetic susceptibility for the formation of copper(II)-complexes from a copper(I) salt. The dimeric nature of the complexes, except that of bis(histidinato)copper(II), was confirmed by the lower magnetic-moments (1.40–1.50 BM) than the spin only value (1.73 BM).

Range-separated hybrid van der Waals density functionals to describe Cu[formula omitted]O[formula omitted]-complexes

Dimeric copper centers are commonly used to activate molecular oxygen in enzymatic and heterogeneous catalysis where Cu2 is embedded in porous structures. Here we evaluate the ability of recently developed range-separated hybrid van der Waals density functionals to describe activated O2 in a crystal with the Cu2O2 unit and in a ▪ complex embedded in a chabzite zeolite. The electronic and geometrical structure of the Cu2O2 unit depends sensitively on the exchange–correlation functional and a sufficiently large amount of short-ranged Fock-exchange is needed to describe the experimentally observed Cu2O2 structures.

Relativistic Coupled Cluster with Completely Renormalized and Perturbative Triples Corrections.

We have implemented noniterative triples corrections to the energy from coupled-cluster with single and double excitations (CCSD) within the 1-electron exact two-component (1eX2C) relativistic framework. The effectiveness of both the CCSD(T) and the completely renormalized (CR) CC(2,3) approaches are demonstrated by performing all-electron computations of the potential energy curves and spectroscopic constants of copper, silver, and gold dimers in their ground electronic states. Spin-orbit coupling effects captured via the 1eX2C framework are shown to be crucial for recovering the correct shape of the potential energy curves, and the correlation effects due to triples in these systems change the dissociation energies by about 0.1-0.2 eV or about 4-7%. We also demonstrate that relativistic effects and basis set size and contraction scheme are significantly more important in Au2 than in Ag2 or Cu2.

Spatially asymmetrical copper dimer in ceria as an efficiently synergistic oxidation catalyst

Accurate and facile construction of atomically dispersed active sites is fundamentally important in heterogeneous catalysis. Herein, by applying a unique H2-He pretreatment, we successfully synthesize spatially asymmetrical dimeric Cu stabilized by CeO2. Integrated microscopic and spectroscopic characterizations, together with DFT calculations have revealed the redispersion of Cu species on CeO2 support is accompanied by the formation of Cu dimers with one Cu atom embedded into CeO2 lattice and the neighboring Cu atom supported on-top. The obtained dual-Cu atom catalyst demonstrates its general applicability in emission control scenarios or hydrogen fuel cell for automobile applications with excellent performances. Ab initio calculations reveal that such dimeric Cu sites on CeO2 promote reactant adsorption and lattice oxygen activation, owing to the synergistic effect of unique dimeric Cu structure. This work highlights the great potential of gas pretreatment in the fabrication of dual-atom catalysts, which is widely applicable to active site modulation in advanced oxidation catalysts.

A (2-(Pyrrolidin-1-yl)ethan-1-olate)(1-oxo-3-phenyl-1,4-dihydronaphthalen-2-olate) μ-Oxo-Bridged Dicopper(II) Dimeric Complex

The reaction of 2-(1H-pyrrol-1-yl)ethanol with 3-hydroxyflavone in the presence of copper(II) bromide yielded a dimeric copper(II) complex, [μ-O-(κ2-O,O-flav)(κ2-N,O-2PEO)Cu]2 (1) (flav = 3-hydroxyflavonolate; 2PEO = 2-(1H-pyrrol-1-yl)ethanolate) with both the flav and 2PEO ligands bound to the copper(II) atom in a κ2-bonding mode. The dimer is held electrostatically by bridging oxygen atoms between two copper atoms. Complex 1 was characterized by single-crystal X-ray diffraction, infrared, and UV-Vis spectroscopy, elemental analysis, and melting point determination. The complex crystallizes in the monoclinic space group P21/n (14) with cell values of a = 11.85340(10) Å, b = 8.51480(10) Å, c = 23.8453(2) Å; β = 99.3920(10)°.

Supramolecular hydrogen-bonded networks formed from copper(II) carboxylate dimers.

The well-known copper carboxylate dimer, with four carboxylate ligands extending outwards towards the corners of a square, has been employed to generate a series of crystalline compounds. In particular, this work centres on the use of the 4-hydroxybenzoate anion (Hhba-) and its deprotonated phenolate form 4-oxidobenzoate (hba2-) to obtain complexes with the general formula [Cu2(Hhba)4-x(hba)xL2-y]x-, where L is an axial coligand (including solvent molecules), x = 0, 1 or 2, and y = 0 or 1. In some cases, short hydrogen bonds result in complexes which may be represented as [Cu2(Hhba)2(H0.5hba)2L2]-. The main focus of the investigation is on the formation of a variety of extended networks through hydrogen bonding and, in some crystals, coordinate bonds when bridging coligands (L) are employed. Crystals of [Cu2(Hhba)4(dioxane)2]·4(dioxane) consist of the expected Cu dimer with the Hhba- anions forming hydrogen bonds to 1,4-dioxane molecules which block network formation. In the case of crystals of composition [Et4N][Cu2(Hhba)2(H0.5hba)2(CH3OH)(H2O)]·2(dioxane), Li[Cu2(Hhba)2(H0.5hba)2(H2O)2]·3(dioxane)·4H2O and [Cu2(Hhba)2(H0.5hba)2(H0.5DABCO)2]·3CH3OH (DABCO is 1,4-diazabicyclo[2.2.2]octane), square-grid hydrogen-bonded networks are generated in which the complex serves as one type of 4-connecting node, whilst a second 4-connecting node is a hydrogen-bonding motif assembled from four phenol/phenolate groups. Another two-dimensional (2D) network based upon a related square-grid structure is formed in the case of [Et4N]2[Cu2(Hhba)2(hba)2(dioxane)2][Cu2(Hhba)4(dioxane)(H2O)]·CH3OH. In [Cu2(Hhba)4(H2O)2]·2(Et4NNO3), a square-grid structure is again apparent, but, in this case, a pair of nitrate anions, along with four phenolic groups and a pair of water molecules, combine to form a second type of 4-connecting node. When 1,8-bis(dimethylamino)naphthalene (bdn, `proton sponge') is used as a base, another square-grid network is generated, i.e. [Hbdn]2[Cu2(Hhba)2(hba)2(H2O)2]·3(dioxane)·H2O, but with only the copper dimer complex serving as a 4-connecting node. Complex three-dimensional networks are formed in [Cu2(Hhba)4(O-bipy)]·H2O and [Cu2(Hhba)4(O-bipy)2]·2(dioxane), where the potentially bridging 4,4'-bipyridine N,N'-dioxide (O-bipy) ligand is employed. Rare cases of mixed carboxylate copper dimer complexes were obtained in the cases of [Cu2(Hhba)3(OAc)(dioxane)]·3.5(dioxane) and [Cu2(Hhba)2(OAc)2(DABCO)2]·10(dioxane), with each structure possessing a 2D network structure. The final compound reported is a simple hydrogen-bonded chain of composition (H0.5DABCO)(H1.5hba), formed from the reaction of H2hba and DABCO.

Morphological studies, photocatalytic degradation of organic dyes and anticancer potential of copper sulfide nanoparticles prepared from bis(diallyl dithiocarbamato)copper(II) complex

Bis(diallyl dithiocarbamato)copper(II) complex was synthesized and characterized by single crystal X-ray crystallography. The molecular structure revealed dimeric copper(II) complex consisting of two copper(II) ions that coordinate two molecules of diallydithiocarbamato anions in bidentate chelating modes and the centrosymmetrically related diallydithiocarbamato anions bridges the S-atom of the adjacent chelating ligand to formed square pyramidal geometry around the copper(II) ions. Copper sulfide nanoparticles were prepared at 160 °C by thermolysis of the copper(II) complex in dodecylamine (DDA), hexadecylamine (HDA), and octadecylamine (ODA) to study the effect of capping agents on the structural morphologies, photocatalytic properties, and anticancer potential of the as-prepared copper sulfides nanoparticles. Powder X-ray diffraction patterns confirmed Cu9S5 digenite crystalline phases for CuS-DDA and CuS-HDA while CuS-ODA is covellite crystalline phase. HRTEM images showed spherical particles with particle sizes in the range 2–25 nm. The copper sulfide nanophotocatalysts are efficient for the degradation of bromophenol blue with the highest photocatalytic efficiency of 95.14 % for CuS-DDA followed by CuS-HDA with 94.52 % and 93.95 % for CuS-ODA. The anticancer potentials of the compounds showed that CuS-HDA is the most potent with IC50 values of 1.22 µg/mL against HEK293 and 28.78 µg/mL against HeLa.

Magnetic Exchange Coupling in Zeolite Copper Dimers and Its Contribution to Methane Activation.

The highly reactive binuclear [Cu2O]2+ active site in copper zeolites activates the inert C-H bond of methane at low temperatures, offering a potential solution to reduce methane flaring and mitigate atmospheric methane levels. While substantial progress has been made in understanding the activation of methane by this core, one critical aspect, the active site's spin, has remained undetermined. In this study, we use variable-temperature, variable-field magnetic circular dichroism spectroscopy to define the ground state spin of the [Cu2O]2+ active sites in Cu-CHA and Cu-MFI. This novel approach allows for site-selective determination of the magnetic exchange coupling between the two copper centers of specific [Cu2O]2+ cores in a heterogeneous mixture, circumventing the drawbacks of bulk magnetic techniques. These experimental findings are coupled to density functional theory calculations to elucidate magnetostructural correlations in copper zeolites that are different from those of homogeneous binuclear Cu(II) complexes. The different spin states for the [Cu2O]2+ cores have different reactivities governed by how methane approaches the active site. This introduces a new understanding of zeolite topological control on active site reactivity.

Competition between Cu-Br semi-coordinate bond and C-H∙∙∙Br, C-H∙∙∙S and S∙∙∙S interactions; new two thioalkylazothiophenol (SNS) copper (II) dimers [Cu(L)(µ-Br)

Two new copper dimers [Cu(L)(µ-Br)]2, HL = 2(RS)C6H4N = NC(COCH3)-SC6H5, where R = CH3 (1), C6H5 (2) were synthesized and characterized using a variety of physicochemical methods, including single crystal X-ray diffraction. The molecular structures of the two binuclear copper(II) complexes show that Cu∙∙∙Cu inter-nuclei distances are 3.662 \\AA and 3.392 \\AA in 1 and 2, respectively. Structural analysis of the two dimers supported by QTAIM analysis of electron density indicates the presence of competition between Cu∙∙∙Br semi-coordinate bond and CH∙∙∙Br and CH∙∙∙S hydrogen bonding interactions and S∙∙∙S chalcogen bonding interactions. In complex 1, CH∙∙∙Br and CH∙∙∙S hydrogen bonding interactions exist, in contrast, they are absent in 2. Cu∙∙∙Br semi-coordinate bonds are stronger in 2 as indicated by Cu∙∙∙Br bond distances; Cu∙∙∙Br bond distances are 2.955 and 2.858 Å in 1 and 2.746 Å in 2. There are two weaker S∙∙∙S interactions in 2 and one stronger interaction in 1 as indicated by S∙∙∙S interatomic distances. The two copper dimers and their ligands exhibited good anticancer efficacy against breast (MCF-7), lung (HCT115), and colon human (A549) cancer cell lines. Complex 1 demonstrated strong cancer cell death compared to complex 2. Additionally, the complexes exhibited higher activity than the ligands. Dimer 2 exhibits two quasi-reversible one-electron reduction waves at −0.05 V and −0.37 V. The comproportionating constant for forming the Cu(I/II) mixed-valence complex was 2.57 × 105. The absence of Intervalence transfer (IT) bands in the electronic absorption spectrum for the mixed-valence complex suggested that a single unpaired electron is localized on one copper center.

New copper carboxyl-ate pyrene dimers: synthesis, crystal structure, Hirshfeld surface analysis and electrochemical characterization.

Two new copper dimers, namely, bis-(dimethyl sulfoxide)-tetra-kis-(μ-pyrene-1-carboxyl-ato)dicopper(Cu-Cu), [Cu2(C17H9O2)4(C2H6OS)2] or [Cu2(pyr-COO-)4(DMSO)2] (1), and bis-(di-methyl-formamide)-tetra-kis-(μ-pyrene-1-carboxyl-ato)dicopper(Cu-Cu), [Cu2(C17H9O2)4(C3H7NO)2] or [Cu2(pyr-COO-)4(DMF)2] (2) (pyr = pyrene), were synthesized from the reaction of pyrene-1-carb-oxy-lic acid, copper(II) nitrate and tri-ethyl-amine from solvents DMSO and DMF, respectively. While 1 crystallized in the space group P , the crystal structure of 2 is in space group P21/n. The Cu atoms have octa-hedral geometries, with four oxygen atoms from carboxyl-ate pyrene ligands occupying the equatorial positions, a solvent mol-ecule coordinating at one of the axial positions, and a Cu⋯Cu contact in the opposite position. The packing in the crystal structures exhibits π-π stacking inter-actions and short contacts through the solvent mol-ecules. The Hirshfeld surfaces and two-dimensional fingerprint plots were generated for both compounds to better understand the inter-molecular inter-actions and the contribution of heteroatoms from the solvent ligands to the crystal packing. In addition, a Cu2+/Cu1+ quasi-reversible redox process was identified for compound 2 using cyclic voltammetry that accounts for a diffusion-controlled electron-donation process to the Cu dimer.

Bipartite entanglement via distance between the states in a one dimensional spin 1/2 dimer copper acetate monohydrate

In this paper, we used a theoretical measure known as distance between the states, , to determine the bipartite entanglement of a one dimensional magnetic dimer system. The calculation was compared with the well-known entanglement measure, concurrence, and found to be the same. was, then, expressed in terms of two thermodynamic quantities, namely, magnetic susceptibility and specific heat. Experimental verification of temperature variation of the bipartite entanglement measure in terms of magnetic susceptibility and specific heat was done on single crystals of copper acetate-an excellent one dimensional dimer system. The results showed the existence of bipartite entanglement till temperatures as high as room temperature! Large sized single crystals of copper acetate were grown by a new evaporation technique and characterised by thermogravimetric analysis, IR and Raman spectroscopy measurements. Density functional theory calculations were done to calculate the delocalisation index which showed much lower values of than other bonds, implying that the probability of direct Cu–Cu exchange in copper acetate is very small. Band structure calculations revealed the presence of flat bands at the Fermi level implying very weak intermolecular interactions in copper acetate.

Coordinated solvent-controlled assembly of a novel NbO-type MOF containing diiron paddle-wheel units: Synthesis, crystal structure, and magnetic property

A novel NbO-type Fe-MOF, named [FeIIFeIII(BPTC)(DMSO)2]·Cl·DMA·DMSO] (SQNU-56, SQNU = Shangqiu Normal University), was successfully synthesized using a specific solvent ratio of DMA/DMSO/HBF4. Structural analysis shows that SQNU-56 is isostructural with the MOF-505, with except for the DMSO coordinated diiron paddle-wheel unit replacing the H2O coordinated dimeric copper paddle-wheel unit. Interestingly, the results of the magnetic investigation demonstrate that SQNU-56 is a promising candidate material for magnetic application.

Robust Proton Conduction against Mechanical Stress in Flexible Free‐Standing Membrane Composed of Two‐Dimensional Coordination Polymer

AbstractIntroduction of mechanical flexibility into proton‐conducting coordination polymers (CPs) is in high demand for future protonic applications such as fuel cells and hydrogen sensors. Although such mechanical properties have been primarily investigated in one‐dimensional (1D) CPs, in this study, we successfully fabricated highly flexible free‐standing CP membranes with a high surface‐to‐volume ratio, which is beneficial for enhanced performance in the aforementioned applications. We fabricated a layered CP, Cu2(NiTCPP) (H4(H2TCPP); 5,10,15,20‐tetrakis(4‐carboxyphenyl) porphyrin), in which a two‐dimensional (2D) square grid sheet composed of tetradentate nickel porphyrins and paddlewheel‐type copper dimers was connected to each other by weak van der Waals forces. The mechanical flexibility was evaluated by bending and tensile tests. The flexural and Young's moduli of the membrane were significantly higher than those of conventional Nafion membranes. Electrochemical impedance spectroscopy analysis revealed that the in‐plane proton conductivity of the membrane was maintained even under applied bending stress. Because the X‐ray diffraction analysis indicates that the proton‐conducting pathway through the hydrogen bonding network remains intact during the bending operation, our present study provides a promising strategy for the fabrication of new and advanced 2D CPs without using substrates or additional polymers for protonic devices.

Robust Proton Conduction against Mechanical Stress in Flexible Free-Standing Membrane Composed of Two-Dimensional Coordination Polymer.

Introduction of mechanical flexibility into proton-conducting coordination polymers (CPs) is in high demand for future protonic applications such as fuel cells and hydrogen sensors. Although such mechanical properties have been primarily investigated in one-dimensional (1D) CPs, in this study, we successfully fabricated highly flexible free-standing CP membranes with a high surface-to-volume ratio, which is beneficial for enhanced performance in the aforementioned applications. We fabricated a layered CP, Cu2 (NiTCPP) (H4 (H2 TCPP); 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin), in which a two-dimensional (2D) square grid sheet composed of tetradentate nickel porphyrins and paddlewheel-type copper dimers was connected to each other by weak van der Waals forces. The mechanical flexibility was evaluated by bending and tensile tests. The flexural and Young's moduli of the membrane were significantly higher than those of conventional Nafion membranes. Electrochemical impedance spectroscopy analysis revealed that the in-plane proton conductivity of the membrane was maintained even under applied bending stress. Because the X-ray diffraction analysis indicates that the proton-conducting pathway through the hydrogen bonding network remains intact during the bending operation, our present study provides a promising strategy for the fabrication of new and advanced 2D CPs without using substrates or additional polymers for protonic devices.

Synthesis and Characterization of a New Cu(II) Paddle-Wheel-like Complex with 4-Vinylbenzoate as an Inorganic Node for Metal–Organic Framework Material Design

A new Cu(II) paddle-wheel-like complex with 4-vinylbenzoate was synthesized using acetonitrile as the solvent. The complex was characterized by X-ray crystal diffraction, FT-IR, diffuse reflectance spectroscopy, thermogravimetric, differential scanning calorimetric, magnetic susceptibility, and electronic paramagnetic resonance analyses. The X-ray crystal diffraction analysis indicated that each copper ion was bound at an equatorial position to four oxygen atoms from the carboxylate groups of the 4-vinylbenzoate ligand in a square-based pyramidal geometry. The distance between the copper ions was 2.640(9) Å. The acetonitrile molecules were coordinated at the axial position to the copper ions. Exposure of the Cu(II) complex to humid air promoted the gradual replacement of the coordinated acetonitrile by water molecules, but the complex structure integrity remained. The EPR spectra exhibited signals attributed to the presence of a mixture of the monomeric (S = ½) and dimeric (S = 1) copper species in a possible 3:1 ratio. The magnetic studies revealed a peak at 50–100 K, which could be associated with the oxygen absorption capacity of the Cu(II)–vba complex.

Fragmentation of and electron detachment from hot copper and silver dimer anions: A comparison

Fragmentation of and electron detachment from hot copper and silver dimer anions: A comparison

Substitutional Coinage Metals as Promising Defects for Adsorption and Detection of Gases on MoS2 Monolayers: A Computational Approach.

Defective molybdenum disulfide (MoS2) monolayers (MLs) modified with coinage metal atoms (Cu, Ag and Au) embedded in sulfur vacancies are studied at a dispersion-corrected density functional level. Atmospheric constituents (H2, O2 and N2) and air pollutants (CO and NO), known as secondary greenhouse gases, are adsorbed on up to two atoms embedded into sulfur vacancies in MoS2 MLs. The adsorption energies suggest that the NO (1.44 eV) and CO (1.24 eV) are chemisorbed more strongly than O2 (1.07 eV) and N2 (0.66 eV) on the ML with a cooper atom substituting for a sulfur atom. Therefore, the adsorption of N2 and O2 does not compete with NO or CO adsorption. Besides, NO adsorbed on embedded Cu creates a new level in the band gap. In addition, it was found that the CO molecule could directly react with the pre-adsorbed O2 molecule on a Cu atom, forming the complex OOCO, via the Eley-Rideal reaction mechanism. The adsorption energies of CO, NO and O2 on Au2S2, Cu2S2 and Ag2S2 embedded into two sulfur vacancies were competitive. Charge transference occurs from the defective MoS2 ML to the adsorbed molecules, oxidizing the later ones (NO, CO and O2) since they act as acceptors. The total and projected density of states reveal that a MoS2 ML modified with copper, gold and silver dimers could be used to design electronic or magnetic devices for sensing applications in the adsorption of NO, CO and O2 molecules. Moreover, NO and O2 molecules adsorbed on MoS2-Au2s2 and MoS2-Cu2s2 introduce a transition from metallic to half-metallic behavior for applications in spintronics. These modified monolayers are expected to exhibit chemiresistive behavior, meaning their electrical resistance changes in response to the presence of NO molecules. This property makes them suitable for detecting and measuring NO concentrations. Also, modified materials with half-metal behavior could be beneficial for spintronic devices, particularly those that require spin-polarized currents.

Transformation of a copper complex to a 1-D coordination polymer to 3-D metal-organic frameworks

A new copper complex and two new copper coordination polymers were synthesized and transformed into metal-organic frameworks (MOFs). The copper polymer, Cu[(4–3-pbz)2(H2O)] (1), coordinates copper and 4-(3-pyridyl) benzoate and water molecules. The copper complex, Cu2[(4–2-pbz)4(DMF)2] (2), which forms a paddlewheel copper dimer coordinated with 4-(2-pyridyl)benzoate and DMF molecules, was used to form a secondary copper polymer, Cu2[(bpy)(Acetate)4] ּ THF (3). The paddlewheel dimer motif was retained and was used as a metalloligand. It was reacted with the linkers, terephthalic acid (BDC) and 4-biphenyl dicarboxylic acid (BPDC), individually, to synthesize two MOFs.

Structural Evolution of Copper-Oxo Sites in Zeolites upon the Reaction with Methane Investigated by Means of Cu K-edge X-ray Absorption Spectroscopy

The structure of copper sites formed under an oxidative environment and their evolution in the course of the reaction with methane at elevated temperature was investigated by means of Cu K-edge X-ray absorption spectroscopy for a series of copper-containing MFI, MOR, and FAU zeolites. The pretreatment in oxygen at 723 K leads to the formation of copper(II)-oxo sites, whose nature depends on the framework type. Dimeric species are formed in CuMFI material, dimeric and monomeric sites coexist in CuMOR, and agglomerated copper-oxo nanoclusters are found in large-pore copper-containing faujasite (CuFAU). For all studied materials, the reaction with methane resulted in the exclusive formation of copper(I) species; no formation of metallic copper was detected even at 748 K. The nature of formed copper(I) species is governed by the structure of corresponding copper(II) centers. In particular, monomeric and dimeric copper(II)-oxo sites hosted in CuMOR and CuMFI are transformed into isolated copper(I) cations coordinated to ion-exchange positions of the zeolite. Contrarily, copper(II)-oxo clusters present in CuFAU undergo restructuring with only a partial loss of extra-framework oxygen and form aggregated species with a structure similar to that of bulk copper(I) oxide.

Less-Coordinated Atomic Copper-Dimer Boosted Carbon-Carbon Coupling During Electrochemical CO2 Reduction.

This work reports a metal-organic framework (MOF) with less-coordinated copper dimers, which displays excellent electrochemical CO2 reduction (eCO2 RR) performance with an advantageous current density of 0.9 A cm-2 and a high Faradaic efficiency of 71% to C2 products. In comparison with MOF with Cu monomers that are present as Cu1 O4 with a coordination number of 3.8 ± 0.2, Cu dimers exist as O3 Cu1 ···Cu2 O2 with a coordination number of 2.8 ± 0.1. In situ characterizations together with theoretical calculations reveal that two *CO intermediates are stably adsorbed on each site of less-coordinated Cu dimers, which favors later dimerization via a key intermediate of *CH2 CHO. The highly unsaturated dual-atomic Cu provides large-quantity and high-quality actives sites for carbon-carbon coupling, achieving the optimal trade-off between activity and selectivity of eCO2 RR to C2 products.