Highly active catalysts: Double‐shelled hollow nanospheres with tiny Pt NPs

A facile strategy was reported to fabricate a novel Pt‐based metal oxide double‐shelled hollow nanospheres (MDSHs), which avoided the traditional tedious procedures. It was attractive that the formation mechanism of DSHs involved redeposition of etch‐released silica species and self‐assembly of metal oxide units. To verify the successful synthesis and structure features of Pt‐LCDSHs catalyst, the as‐prepared samples were characterized by several techniques, such as SEM, N₂ adsorption–desorption isotherm analysis, TEM, EDX, XRD and XPS. Results indicated that all of MDSHs possessed double‐shelled structures with both the inner and outer shells composing of metal oxide units. Interestingly, the metal oxide of the DHSs could offer abundant active points for Pt NPs and the space between the double shells also could be filled with Pt NPs. What's more, compared with the pure samples, the Pt‐embedded La₂O₃‐CeO₂‐DSHs exhibited the highest catalytic performance (6.58 × 10^?3 min^?1) and good reusability with a conversion of 94% even after eight cycles, which were evaluated by means of the reduction of 4‐nitrophenol monitored by UV–vis spectra. Finally, a possible reaction mechanism for the reduction reaction on Pt‐based La₂O₃‐CeO₂‐DSHs was also proposed.     

Effective,Low‐Cost Recovery of Toxic Arsenate Anions from Water by Using Hollow‐Sphere Geode Traps

Because of the devastating impact of arsenic on terrestrial and aquatic organisms, the recovery, removal, disposal, and management of arsenic‐contaminated water is a considerable challenge and has become an urgent necessity in the field of water treatment. This study reports the controlled fabrication of a low‐cost adsorbent based on microscopic C‐,N‐doped NiO hollow spheres with geode shells composed of poly‐CN nanospherical nodules (100 nm) that were intrinsically stacked and wrapped around the hollow spheres to form a shell with a thickness of 500–700 nm. This C‐,N‐doped NiO hollow‐sphere adsorbent (termed CNN) with multiple diffusion routes through open pores and caves with connected open macro/meso windows over the entire surface and well‐dispersed hollow‐sphere particles that create vesicle traps for the capture, extraction, and separation of arsenate (AsO₄³⁻) species from aqueous solution. The CNN structures are considered to be a potentially attractive adsorbent for AsO₄³⁻ species due to 1) superior removal and trapping capacity from water samples and 2) selective trapping of AsO₄³⁻ from real water samples that mainly contained chloride and nitrate anions and Fe²⁺, and Mn²⁺, Ca²⁺, and Mg²⁺ cations. The structural stability of the hierarchal geodes was evident after 20 cycles without any significant decrease in the recovery efficiency of AsO₄³⁻ species. To achieve low‐cost adsorbents and toxic‐waste management, this superior CNN AsO₄³⁻ dead‐end trapping and recovery system evidently enabled the continuous control of AsO₄³⁻ disposal in water‐scarce environments, presents a low‐cost and eco‐friendly adsorbent for AsO₄³⁻ species, and selectively produced water‐free arsenate species. These CNN geode traps show potential as excellent adsorbent candidates in environment remediation tools and human healthcare.     

One‐Step Synthesis of Small‐Sized and Water‐Soluble NaREF4 Upconversion Nanoparticles for In Vitro Cell Imaging and Drug Delivery

Small (2–28 nm) NaREF₄ (rare earth (RE)=Nd–Lu, Y) nanoparticles (NPs) were prepared by an oil/water two‐phase approach. Meanwhile, hydrophilic NPs can be obtained through a successful phase‐transition process by introducing the amphiphilic surfactant sodium dodecylsulfate (SDS) into the same reaction system. Hollow‐structured NaREF₄ (RE=Y, Yb, Lu) NPs can be fabricated in situ by electron‐beam lithography on solid NPs. The MTT assay indicates that these hydrophilic NPs with hollow structures exhibit good biocompatibility. The as‐prepared hollow‐structured NPs can be used as anti‐cancer drug carriers for drug storage/release investigations. Doxorubicin hydrochloride (DOX) was taken as model drug. The release of DOX from hollow α‐NaLuF₄:20 % Yb³⁺, 2 % Er³⁺ exhibits a pH‐sensitive release patterns. Confocal microscopy observations indicate that the NPs can be taken up by HeLa cells and show obvious anti‐cancer efficacy. Furthermore, α‐NaLuF₄:20 % Yb³⁺, 2 % Er³⁺ NPs show bright‐red emission under IR excitation, making both the excitation and emission light fall within the “optical window” of biological tissues. The application of α‐NaLuF₄:20 % Yb³⁺, 2 % Er³⁺ in the luminescence imaging of cells was also investigated, which shows a bright‐red emission without background noise.     

Synthesis of Hollow Mesoporous TiO2 Microspheres with Single and Double Au Nanoparticle Layers for Enhanced Visible‐Light Photocatalysis

A facile method was used to prepare hollow mesoporous TiO₂ and Au@TiO₂ spheres using polystyrene (PS) templates. Au nanoparticles (NPs) were simultaneously synthesized and attached on the surface of PS spheres by reducing AuCl₄^? ions using sodium citrate which resulted in the uniform deposition of Au NPs. The outer coating of titania via sol‐gel produced PS@Au@TiO₂ core–shell spheres. Removing the templates from these core–shell spheres through calcination produced hollow mesoporous and crystalline Au@TiO₂ spheres with Au NPs inside the TiO₂ shell in a single step. Anatase spheres with double Au NPs layers, one inside and another outside of TiO₂ shell, were also prepared. Different characterization techniques indicated the hollow mesoporous and crystalline morphology of the prepared spheres with Au NPs. Hollow anatase spheres with Au NPs indicated enhanced harvesting of visible light and therefore demonstrated efficient catalytic activity toward the degradation of organic dyes under the irradiation of visible light as compared to bare TiO₂ spheres.     

Novel synthesis of Fe2O3–Pt ellipsoids coated by double‐shelled La2O3 as a catalyst for the reduction of 4‐nitrophenol

A facile strategy is reported for the fabrication of Pt‐loaded core–shell nanocomposite ellipsoids (Fe₂O₃‐Pt@DSL) consisting of ellipsoidal Fe₂O₃ cores, double‐layered La₂O₃ shells and deposited Pt nanoparticles (NPs). The formation of the doubled‐shelled structure uses Fe₂O₃‐Pt@mSiO₂ as template sacrificial agent and it involves the re‐deposition of silica and self‐assembly of metal oxide units. The preparation methods of double‐shelled metal oxides avoid repeated coating and etching and could be utilized to fabricate other shaped double‐shelled composites. Characterization results indicated that the Fe₂O₃‐Pt@DSL nanocomposites possessed mesoporous structure and tunable shell thickness. Moreover, due to the formation of Fe₂O₃ and La₂O₃ composites, Pt NPs can also be stabilized via deposition on chemically active oxides with a synergistic effect. Therefore, as a catalyst for the reduction of 4‐nitrophenol, Fe₂O₃‐Pt@DSL showed superior catalytic activity and reusability due to structural superiority and enhanced composite synergy. Finally, well‐dispersed Pt NPs were encapsulated into the void between the shell layers to construct the Fe₂O₃‐Pt@DSL‐Pt catalyst.     

Rare‐Earth‐Based Nanoparticles with Simultaneously Enhanced Near‐Infrared (NIR)‐Visible (Vis) and NIR‐NIR Dual‐Conversion Luminescence for Multimodal Imaging

Multifunctional NaGdF₄:Yb³⁺,Er³⁺,Nd³⁺@NaGdF₄:Nd³⁺ core–shell nanoparticles (called Gd:Yb³⁺,Er³⁺,Nd³⁺@Gd:Nd³⁺ NPs) with simultaneously enhanced near‐infrared (NIR)‐visible (Vis) and NIR‐NIR dual‐conversion (up and down) luminescence (UCL/DCL) properties were successfully synthesized. The resulting core–shell NPs simultaneously emitted enhanced UCL at 522, 540, and 660 nm and DCL at 980 and 1060 nm under the excitation of a 793 nm laser. The enhanced UCL and DCL can be explained by complex energy‐transfer processes, Nd³⁺→Yb³⁺→Er³⁺ and Nd³⁺→Yb³⁺, respectively. The effects of Nd³⁺ concentration and shell thickness on the UCL/DCL properties were systematically investigated. The UCL and DCL properties of NPs were observed under the optimal conditions: a shell Nd³⁺ content of 20 % and a shell thickness of approximately 5 nm. Moreover, the Gd:Yb³⁺,Er³⁺,Nd³⁺@Gd:20 % Nd³⁺ NPs exhibited remarkable magnetic resonance imaging (MRI) properties similar to that of a clinical agent, Omniscan. Thus, the core–shell NPs with excellent UCL/DCL/magnetic resonance imaging (MRI) properties have great potential for both in vitro and in vivo multimodal bioimaging.     

General Synthesis of Multi‐Shelled Mixed Metal Oxide Hollow Spheres with Superior Lithium Storage Properties

Complex hollow structures of transition metal oxides, especially mixed metal oxides, could be promising for different applications such as lithium ion batteries. However, it remains a great challenge to fabricate well‐defined hollow spheres with multiple shells for mixed transition metal oxides. Herein, we have developed a new “penetration–solidification–annealing” strategy which can realize the synthesis of various mixed metal oxide multi‐shelled hollow spheres. Importantly, it is found that multi‐shelled hollow spheres possess impressive lithium storage properties with both high specific capacity and excellent cycling stability. Specifically, the carbon‐coated CoMn₂O₄ triple‐shelled hollow spheres exhibit a specific capacity of 726.7 mA h g^?1 and a nearly 100 % capacity retention after 200 cycles. The present general strategy could represent a milestone in design and synthesis of mixed metal oxide complex hollow spheres and their promising uses in different areas.     

Simultaneous removal of Cu2+ and Cr3+ ions from aqueous solution based on Complexation with Eriochrome cyanine‐R and derivative spectrophotometric method

TiO₂ nanoparticles deposited on activated carbon (TiO₂–NP–AC) was prepared and characterized by XRD and SEM analysis. Subsequently, simultaneous ultrasound‐assisted adsorption of Cu²⁺ and Cr³⁺ ions onto TiO₂‐NPs‐AC after complexation via eriochrome cyanine R (ECR) has been investigated with UV–Vis and FAA spectrophotometer. Spectra overlapping of the ECR‐Cu and ECR‐Cr complex was resolve by derivative spectrophotometric technique. The effects of various parameters such as initial Cu²⁺ (A) and Cr³⁺ (B) ions concentrations, TiO₂‐NPs‐AC mass (C), sonication time (D) and pH (E) on the removal percentage were investigated and optimized by central composite design (CCD). The optimize conditions were set as: 4.21 min, 0.019 mg, 20.02 and 13.22 mg L^?1 and 6.63 for sonication time, TiO₂–NP–AC mass, initial Cr³⁺ and Cu²⁺ ions concentration and pH, respectively. The experimental equilibrium data fitting to Langmuir, Freundlich, Temkin and Dubinin–Radushkevich models show that the Langmuir model is a good and suitable model for evaluation and the actual behavior of adsorption process and maximum adsorption capacity of 105.26 and 93.46 mg g^?1 were obtained for Cu²⁺ and Cr³⁺ ions, respectively. Kinetic evaluation of experimental data showed that the adsorption processes followed well pseudo second order and intraparticle diffusion models.     

Magnetically recyclable nano copper/chitosan in O‐arylation of phenols with aryl halides

Interaction of chitosan (CS) with Fe₃O₄, followed by embedding Cu nanoparticles (NPs) on the magnetic surface through adsorption of Cu²⁺, and its reduction to Cu^o via NaBH₄, offers a reusable efficient catalyst (Fe₃O₄/CS‐Cu NPs) that is employed in cross‐coupling reactions of aryl halides with phenols, which affords the corresponding diaryl ethers, with good to excellent yields. The catalyst is completely recoverable from the reaction mixture by using an external magnet. It can be reused four times, without significant loss in its catalytic activity.     

CuCoO2 Nanoparticles as a Nanoprotease for Selective Proteolysis with High Efficiency at Room Temperature

Many nanoproteases contain tetravalent metal ions and catalyze peptide-bond hydrolysis only at high temperature (60 °C). Here, we report a new and effective strategy to explore nanoproteases from nanoparticles containing low valent metal ions. We found that flower-like CuCoO₂ nanoparticles (CuCoO₂ NPs) containing low valent Cu⁺ possessed excellent catalytic activity towards selective cleavage of peptide bonds with hydrophobic residues in bovine serum albumin (BSA) at room temperature. CuCoO₂ NPs exhibited excellent stability and had great reusability. CuCoO₂ NPs also hydrolyzed heat-denatured and surfactant-denatured BSA. Mechanism analysis revealed that the high Lewis acidity of Co³⁺ and the low valence of Cu⁺ were both essential for the high protease activity of CuCoO₂ NPs. The flower-like structure of CuCoO₂ NPs and the strong nucleophilicity of Cu⁺-bound hydroxyl endow them with excellent catalytic performance. The findings open a new way for the design and discovery of high-efficiency nanoproteases.     

Formation of Triple‐Shelled Molybdenum–Polydopamine Hollow Spheres and Their Conversion into MoO2/Carbon Composite Hollow Spheres for Lithium‐Ion Batteries

Unique triple‐shelled Mo‐polydopamine (Mo‐PDA) hollow spheres are synthesized through a facile solvothermal process. A sequential self‐templating mechanism for the multi‐shell formation is proposed, and the number of shells can be adjusted by tuning the size of the Mo‐glycerate templates. These triple‐shelled Mo‐PDA hollow spheres can be converted to triple‐shelled MoO₂/carbon composite hollow spheres by thermal treatment. Owing to the unique multi‐shells and hollow interior, the as‐prepared MoO₂/carbon composite hollow spheres exhibit appealing performance as an anode material for lithium‐ion batteries, delivering a high capacity of ca. 580 mAh g^?1 at 0.5 A g^?1 with good rate capability and long cycle life.     

The investigation of Ag decorated double‐wall hollow TiO2 spheres as photocatalyst

In this paper, a novel TiO₂ nanosheets assembled double‐wall hollow sphere (DHS)has been prepared successfully via hydrothermal treatment of SiO₂@TiO₂ with the assistant of CTAB.The prepared samples are characterized with transmission electron microscopy (TEM), scanning electron microscopy (SEM), electron spin resonance (ESR), X‐ray diffraction (XRD) and X‐ray photoelectron spectra (XPS), etc.Results show that redeposited silica species play a key role in the formation of the double‐wall structure. The as‐synthesized DHS nanostructure exhibits a large surface area (417.6 m² g^‐1) and excellent mechanical strength. Furthermore, after decoration of Ag and calcination treatment, the double‐shelled TiO₂/Ag heterostructures show an enhanced photocatalytic performance in the degradation of RhB under UV or visible light irradiations for the following reasons: the surface plasmon resonance effect of Ag, strong interaction between Ag and TiO₂ nanosheets, large surface area, excellent adsorption capacityand unique double‐wall structure. On the basis of the experimental results, a possible mechanism for pollutantdegradation under visual light irradiation has been proposed.     

In Situ Fabrication of Inorganic/Organic Hybrid Based on Cu/Co‐ZIF and Cu2O

We successfully fabricate a well‐defined inorganic/organic hybrid Cu₂O@Cu/Co‐ZIF (ZIF=zeolitic imidazolate frameworks) by use of growth of dual‐metal Cu/Co‐ZIF on the obtained Cu₂O hollow spheres. The key point of the strategy is coupling the in situ self‐sacrificing template. Cu₂O and the coordination of metal ions (Cu⁺ and Co²⁺) with 2‐methylimidazole. This new hybrid was characterized by powder X‐ray diffraction, (scanning) transmission electron microscopy, energy‐dispersive spectroscopy mapping, in situ FT‐IR spectroscopy, UV/Vis diffuse reflection spectroscopy, N₂ sorption measurements, and electron spin resonance. It was evidenced that Cu/Co‐ZIF nanocrystals have been assembled to continuous shells surrounding the Cu₂O cores as well as in the voids between layers and inner pores. Cu₂O@Cu/Co‐ZIF exhibits visible light responsiveness and holds potential as narrow band gap semiconductor and visible photocatalyst.     

Confined Nanospace Pyrolysis for the Fabrication of Coaxial Fe3O4@C Hollow Particles with a Penetrated Mesochannel as a Superior Anode for Li‐Ion Batteries

In this study, a method is developed to fabricate Fe₃O₄@C particles with a coaxial and penetrated hollow mesochannel based on the concept of “confined nanospace pyrolysis”. The synthesis involves the production of a polydopamine coating followed by a silica coating on a rod‐shaped β‐FeOOH nanoparticle, and subsequent treatment by using confined nanospace pyrolysis and silica removal procedures. Typical coaxial hollow Fe₃O₄@C possesses a rice‐grain morphology and mesoporous structure with a large specific surface area, as well as a continuous and flexible carbon shell. Electrochemical tests reveal that the hollow Fe₃O₄@C with an open‐ended nanostructure delivers a high specific capacity (ca. 864 mA h g^?1 at 1 A g^?1), excellent rate capability with a capacity of about 582 mA h g^?1 at 2 A g^?1, and a high Coulombic efficiency (>97 %). The excellent electrochemical performance benefits from the hollow cavity with an inner diameter of 18 nm and a flexible carbon shell that can accommodate the volume change of the Fe₃O₄ during the lithium insertion/extraction processes as well as the large specific surface area and open inner cavity to facilitate the rapid diffusion of lithium ions from electrolyte to active material. This fabrication strategy can be used to generate a hollow or porous metal oxide structure for high‐performance Li‐ion batteries.     

Cuprous oxide nanospheres as probes for light scattering imaging analysis of live cells and for conformation identification of proteins

A facile solution-phase synthesis route of highly uniform Cu₂O nanospheres (Cu₂O NPs) with the size of 57.7 ± 4.7 nm was developed, and then the nanoparticles were applied to live cell imaging under a common dark-field microscope. Starting from copper(II) salts, the synthesis of Cu₂O NPs was made in the presence of cetyltrimethylammonium bromide (CTAB) by reducing the copper(II) with sodium borohydride (NaBH₄) in aqueous medium and by aging process in the air. Monitoring of morphology evolution process of Cu₂O NPs with scanning electron microscopy (SEM) and measuring of the UV-visible spectra showed that the synthesis of Cu₂O NPs follows the reduction-oxidation coupled process of Cu²⁺ into Cu⁰ species at first and then the resulted Cu⁰ species into Cu₂O NPs in the air. Light scattering (LS) features have been measured with a common spectrofluorometer and a common dark-field microscope, and it was found that the as-prepared Cu₂O NPs display strong blue scattering light and can be applied for cell imaging. If incubated with human bone marrow neuroblastoma, transferrin-conjugated Cu₂O NPs can get into the cells and show strong pure blue light in cytoplasm. Further investigations showed that the Cu₂O NPs could be applied for probes for conformation of proteins.     

Surface Segregated AgAu Tadpole‐Shaped Nanoparticles Synthesized Via a Single Step Combined Galvanic and Citrate Reduction Reaction

New AgAu tadpole nanocrystals were synthesized in a one‐step reaction involving simultaneous galvanic replacement between Ag nanospheres and AuCl₄^?_(aq.) and AuCl₄^?_(aq.) reduction to Au in the presence of citrate. The AgAu tadpoles display nodular polycrystalline hollow heads, while their undulating tails are single crystals. The unusual morphology suggests an oriented attachment growth mechanism. Remarkably, a 1 nm thick Ag layer was found to segregate so as to cover the entire surface of the tadpoles. By varying the nature of the seeds (Au NPs), double‐headed Au tadpoles could also be obtained. The effect of a number of reaction parameters on product morphology were explored, leading to new insights into the growth mechanisms and surface segregation behavior involved in the synthesis of bimetallic and anisotropic nanomaterials.     

Facile Synthesis of Well‐Dispersed Silver Nanoparticles on Hierarchical Flower‐like Ni3Si2O5(OH)4 with a High Catalytic Activity towards 4‐Nitrophenol Reduction

Layered nickel silicate nanoflowers (NSFs) with a hierarchical nanostructure have been successfully fabricated by a template‐free solvothermal method. The as‐prepared nanoflowers were composed of many interconnected edge‐curving lamellae with a thickness of about 15 nm and had a high specific surface area (279 m² g^?1) and large pore volume (0.67 cm³ g^?1). The highly dispersed small silver nanoparticles (AgNPs) were immobilized on the surface of NSFs through the in situ reduction of Ag⁺ by Sn²⁺. The AgNP/NSF nanocomposites showed a high performance in the catalytic reduction of 4‐nitrophenol. In particular, there was no visible decrease in the catalytic activity of the reused catalysts even after being recycled four times. The as‐prepared AgNP/NSF nanocomposites might be an excellent catalyst owing to their availability, formability, chemical and thermal stability, and high specific surface area.     

Superior Electrochemical Properties of Nanofibers Composed of Hollow CoFe2O4 Nanospheres Covered with Onion‐Like Graphitic Carbon

Nanofibers composed of hollow CoFe₂O₄ nanospheres covered with onion‐like carbon are prepared by applying nanoscale Kirkendall diffusion to the electrospinning process. Amorphous carbon nanofibers embedded with CoFe₂@onion‐like carbon nanospheres are prepared by reduction of the electrospun nanofibers. Oxidation of the CoFe₂‐C nanofibers at 300 °C under a normal atmosphere produces porous nanofibers composed of hollow CoFe₂O₄ nanospheres covered with onion‐like carbon. CoFe₂ nanocrystals are transformed into the hollow CoFe₂O₄ nanospheres during oxidation through a well‐known nanoscale Kirkendall diffusion process. The discharge capacities of the carbon‐free CoFe₂O₄ nanofibers composed of hollow nanospheres and the nanofibers composed of hollow CoFe₂O₄ nanospheres covered with onion‐like carbon are 340 and 930 mA h g^?1, respectively, for the 1000th cycle at a current density of 1 A g^?1. The nanofibers composed of hollow CoFe₂O₄ nanospheres covered with onion‐like carbon exhibit an excellent rate performance even in the absence of conductive materials.     

Tailoring Transition‐Metal Hydroxides and Oxides by Photon‐Induced Reactions

Controlled synthesis of transition‐metal hydroxides and oxides with earth‐abundant elements have attracted significant interest because of their wide applications, for example as battery electrode materials or electrocatalysts for fuel generation. Here, we report the tuning of the structure of transition‐metal hydroxides and oxides by controlling chemical reactions using an unfocused laser to irradiate the precursor solution. A Nd:YAG laser with wavelengths of 532 nm or 1064 nm was used. The Ni²⁺, Mn²⁺, and Co²⁺ ion‐containing aqueous solution undergoes photo‐induced reactions and produces hollow metal‐oxide nanospheres (Ni_0.18Mn_0.45Co_0.37O_x) or core–shell metal hydroxide nanoflowers ([Ni_0.15Mn_0.15Co_0.7(OH)₂](NO₃)_0.2?H₂O), depending on the laser wavelengths. We propose two reaction pathways, either by photo‐induced redox reaction or hydrolysis reaction, which are responsible for the formation of distinct nanostructures. The study of photon‐induced materials growth shines light on the rational design of complex nanostructures with advanced functionalities.     

Oligo-m-phenyleneoxalamide copper(II) mesocates as electro-switchable ferromagnetic metal-organic wires

Double‐stranded copper(II) string complexes of varying nuclearity, from di‐ to tetranuclear species, have been prepared by the Cu^II‐mediated self‐assembly of a novel family of linear homo‐ and heteropolytopic ligands that contain two outer oxamato and either zero ( 1 b ), one ( 2 b ), or two ( 3 b ) inner oxamidato donor groups separated by rigid 2‐methyl‐1,3‐phenylene spacers. The X‐ray crystal structures of these Cu^II_n complexes (n=2 ( 1 d ), 3 ( 2 d ), and 4 ( 3 d )) show a linear array of metal atoms with an overall twisted coordination geometry for both the outer CuN₂O₂ and inner CuN₄ chromophores. Two such nonplanar all‐syn bridging ligands 1 b – 3 b in an anti arrangement clamp around the metal centers with alternating M and P helical chiralities to afford an overall double meso‐helicate‐type architecture for 1 d – 3 d . Variable‐temperature (2.0–300 K) magnetic susceptibility and variable‐field (0–5.0 T) magnetization measurements for 1 d – 3 d show the occurrence of S=nS_Cu (n=2–4) high‐spin ground states that arise from the moderate ferromagnetic coupling between the unpaired electrons of the linearly disposed Cu^II ions (S_Cu=1/2) through the two anti m‐phenylenediamidate‐type bridges (J values in the range of +15.0 to 16.8 cm^?1). Density functional theory (DFT) calculations for 1 d – 3 d evidence a sign alternation of the spin density in the meta‐substituted phenylene spacers in agreement with a spin polarization exchange mechanism along the linear metal array with overall intermetallic distances between terminal metal centers in the range of 0.7–2.2 nm. Cyclic voltammetry (CV) and rotating‐disk electrode (RDE) electrochemical measurements for 1 d – 3 d show several reversible or quasireversible one‐ or two‐electron steps that involve the consecutive metal‐centered oxidation of the inner and outer Cu^II ions (S_Cu=1/2) to diamagnetic Cu^III ones (S_Cu=0) at relatively low formal potentials (E values in the range of +0.14 to 0.25 V and of +0.43 to 0.67 V vs. SCE, respectively). Further developments may be envisaged for this family of oligo‐m‐phenyleneoxalamide copper(II) double mesocates as electroswitchable ferromagnetic ‘metal–organic wires’ (MOWs) on the basis of their unique ferromagnetic and multicenter redox behaviors.