Neutral Copper Research Articles

Copper Iodide Hybrid with Unique Cu3I3 Trimeric Inorganic Functional Unit and Far‐red/Near‐infrared Emission

AbstractIn this paper, a neutral copper iodide hybrid with unique Cu3I3 trimeric inorganic functional unit is successfully fabricated using 5,6,7,8‐tetrahydroquinoxaline (L) with large steric‐hindrance group as the organic ligand. The hybrid owns a one‐dimensional (1D) extended polymeric structure in the form of Cu3I3(L)2. As a CuI‐based hybrid, 1D‐Cu3I3(L)2 has an infrequent far‐red/near‐infrared emission, exhibiting the potential application prospects in the field of display and night vision. Moreover, the luminescence mechanism is carefully studied by decay lifetime measurement and calculation of density of states, which is verified to be the combination of metal‐to‐ligand charge transfer and halide‐to‐ligand charge transfer.

The ground-state structures and spectra of neutral, anionic and cationic copper clusters

The structures and spectra of Cunb (n = 3–16; b = 0, ±1) clusters have been researched by means of density functional theory (DFT) coupled with CALYPSO structure prediction method. It is found that the growth of Cun (n = 9–16) clusters shows a clear regularity. Based on the global minimum structure of the Cun cluster, the UV spectra have been predicted and are in good agreement with the available experimental results. The most stable structures of anionic copper clusters have been identified by comparing experimental and theoretical photoelectron spectra (PES). The infrared (IR) and Raman spectra of cationic copper clusters have been simulated and the calculated IR spectra of Cun+ -Arm (n = 3–10) complexes are in accord with experimental spectra. The Ar atoms adsorbed to small Cun+ cluster have partly influence on the IR spectrum of the host cluster. The Cu6, Cu8 and Cu3+ clusters can be regard as three magic clusters.

Centrosymmetric homo- and heteroleptic core paddle-wheel copper(II) carboxylates; Syntheses, crystal structures, antioxidant, anticancer and enzyme inhibition activity

Synthesis and characterization of homo- (C5H7N2)2[Cu2(3,5-F2C6H3CH2COO)6] (1) and heteroleptic [Cu2(3,5-F2C6H3CH2COO)4(2-CH3Py)2] (2) core paddle-wheel copper(II) carboxylates is reported in the present work. The characterization was made by spectroscopic techniques, elemental and single crystal XRD analyses. The single crystal XRD analysis revealed a rare homoleptic anionic copper(II) carboxylate complex (1) consisting 2-aminopyridinium counter cations and a neutral heteroleptic copper(II) carboxylate complex (2) consisting 2-methyl pyridine as a co-ligand. The copper ions adopted a distorted square pyramidal geometry in both the paddle-wheel dimeric complexes. To evaluate the biological potency of the synthesized complexes, in vitro antioxidant, enzymes inhibition and anticancer activities were performed. The synthesized complexes have shown overall better biological activity compared to the ligand acid. Complex 2 was the most potent DPPH (IC50 =180.96 ± 9.04 µg/mL) and •OH (IC50 = 189.51 ± 9.33 µg/mL) radicals scavenger, α-amylase (IC50 = 441.86 µg/mL) and acetylcholinesterase (IC50 = 88.62 µg/mL) inhibitor. Furthermore, complex 2 activity against malignant glioma U-87 cell line (IC50 = 21.95 µg/mL) was also highest among the tested compounds. However, complex 1 with an IC50 value of 51.83 µg/mL has shown somewhat better inhibition of the butyrylcholinesterase enzyme compared to the complex 2 (IC50 = 56.36 µg/mL).

Copper Soaps Formation in Verdigris-Linseed Oil Painting Mixtures: A Multispectroscopic Characterization.

Copper acetate (also known as verdigris) is a bimetallic Cu(II) greenish pigment widely used in oil paintings. Since ancient times, this pigment has been known as a degradation-prone compound, especially when combined with lipidic binders. However, the degradation mechanism and the involved species have not yet been disclosed. In this article, we study verdigris interactions with linseed oil in painting mock-ups, stressing out the formation of copper-based complexes and proposing reaction routes. Such complex systems are studied by applying a complementary multispectroscopic approach: a combination of continuous-wave (CW) electron paramagnetic resonance (EPR), electron spin echo envelope modulation (ESEEM), and Raman and attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopies. Based on the experimental evidence, we propose the following mechanism: the neutral copper acetate shifts to a basic verdigris-promoting triglyceride hydrolysis, aided by the coordination of Cu(II) cations toward the carboxylic functions. The increased amount of free fatty acids in the mixtures triggers the formation of monomeric Cu(II) complexes. Afterward, the oil polymerization reaction occurs, and secondary oxidation species, containing OH groups in the alkyl chain, act as further ligands for copper nuclei. This is the first time, to the best of our knowledge, that a comprehensive view is proposed.

A Dinuclear Copper(II) Complex Electrochemically Obtained via the Endogenous Hydroxylation of a Carbamate Schiff Base Ligand: Synthesis, Structure and Catalase Activity.

In the present work, we report a neutral dinuclear copper(II) complex, [Cu2(L1)(OH)], derived from a new [N,O] donor Schiff base ligand L1 that was formed after the endogenous hydroxylation of an initial carbamate Schiff base H2L coordinated with copper ions in an electrochemical cell. The copper(II) complex has been fully characterized using different techniques, including X-ray diffraction. Direct current (DC) magnetic susceptibility measurements were also performed at variable temperatures, showing evidence of antiferromagnetic behavior. Its catalase-like activity was also tested, demonstrating that this activity is affected by temperature.

Sub-picosecond photodynamics of small neutral copper oxide clusters.

The ultrafast dynamics of neutral copper oxide clusters (CunOx, n < 5) are reported using femtosecond pump probe spectroscopy in the gas phase. The transient spectra recorded for each cluster demonstrate they relax on a 100s of fs timescale followed by a long-lived (>50 ps) response. Density functional theory calculations are performed to determine the lowest energy structures and spin states. Topological descripters for the excited states are calculated (time-dependent density functional theory) to relate the measured excited state dynamics to changes in the cluster's electronic structure with increasing oxidation. Strong field ionization is demonstrated here to be a soft form of ionization and able to record transient signals for clusters previously determined to be unstable to nanosecond multiphoton ionization. The relative cluster stability is further demonstrated by signal enhancement/depreciation that is recorded through the synergy from the two laser pulses. Once the oxygen atoms exceed the number of copper atoms, a weakly bound superoxide O2 unit forms, exhibiting a higher spin state. All clusters that are not in the lowest spin configuration demonstrate fragmentation.

Analisa Susut Teknis Pada Transformator Distribusi Di Wilayah Kerja PT. PLN (Persero) ULP Bawean

Along with the development of the times, the need for electricity is very necessary. Electrical energy is one of the energy that is needed in using equipment that is related to electrical energy such as household, office and commercial industrial equipment that requires electrical energy. Bawean Island is one of the islands that requires a large amount of electricity due to the growing development of these sectors. With the rapid development of large-scale developments, the need for electricity needs to be increased in order to meet people's demands related to electricity needs. Technical losses are losses that occur for technical reasons where energy is reduced by turning into heat or heat energy. Basically technical losses occur based on energy losses in components caused by errors in the components themselves. Technical losses that occur in distribution transformers are common. In principle, losses always occur because efficiency cannot be 100%. Energy is lost along with distribution from upstream to downstream of distribution transformers. Based on the formulation of the problem taken, the researchers calculated losses at neutral currents, copper losses, total losses, output power and total losses in the form of prices. From the results of the conclusions above, it can be seen that the greater the current in the neutral of the transformer, the more losses that occur in the transformer.

Oxidative addition of an alkyl halide to form a stable Cu(III) product.

The step that cleaves the carbon-halogen bond in copper-catalyzed cross-coupling reactions remains ill defined because of the multiple redox manifolds available to copper and the instability of the high-valent copper product formed. We report the oxidative addition of α-haloacetonitrile to ionic and neutral copper(I) complexes to form previously elusive but here fully characterized copper(III) complexes. The stability of these complexes stems from the strong Cu-CF3 bond and the high barrier for C(CF3)-C(CH2CN) bond-forming reductive elimination. The mechanistic studies we performed suggest that oxidative addition to ionic and neutral copper(I) complexes proceeds by means of two different pathways: an SN2-type substitution to the ionic complex and a halogen-atom transfer to the neutral complex. We observed a pronounced ligand acceleration of the oxidative addition, which correlates with that observed in the copper-catalyzed couplings of azoles, amines, or alkynes with alkyl electrophiles.

Thermally Activated Delayed Fluorescence in Neutral and Cationic Copper(I) Complexes with the 2-(4-Thiazolyl)benzimidazole Ligand.

Cationic [Cu(P^P)(Htbz)]PF6 [P^P = xantphos, dpephos; Htbz = 2-(4-thiazolyl)benzimidazole] and the corresponding neutral complexes [Cu(P^P)(tbz)], obtained through deprotonation of the diimine ligand, have been synthesized with the aim of analyzing the role of the diphosphane and Htbz deprotonation in the emissive properties of these complexes. For the study of the diphosphane effect, the luminescence properties of these compounds have been compared with those of the reported analogous derivatives with Htbz and carborane diphosphanes. Complexes [Cu(P^P)(Htbz)]PF6 (P^P = xantphos, dpephos) and [Cu(dpephos)(tbz)] display thermally activated delayed fluorescence, which has been studied, revealing a ΔE(S1-T1) between 658 and 455 cm-1. Theoretical calculations indicate different origins for the absorptions, leading to the observed emissions.

Columnar Liquid Crystals of Copper(I) Complexes with Ionic Conductivity and Solid State Emission.

Two neutral copper(I) halide complexes ([Cu(BTU)2X], X = Cl, Br) were prepared by the reduction of the corresponding copper(II) halides (chloride or bromide) with a benzoylthiourea (BTU, N-(3,4-diheptyloxybenzoyl)-N'-(4-heptadecafluorooctylphenyl)thiourea) ligand in ethanol. The two copper(I) complexes show a very interesting combination of 2D supramolecular structures, liquid crystalline, emission, and 1D ionic conduction properties. Their chemical structure was ascribed based on ESI-MS, elemental analysis, IR, and NMR spectroscopies (1H and 13C), while the mesomorphic behavior was analyzed through a combination of differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and powder X-ray diffraction (XRD). These new copper(I) complexes have mesomorphic properties and exhibit a hexagonal columnar mesophase over a large temperature range, more than 100 K, as evidenced by DSC studies and POM observations. The thermogravimetric analysis (TG) indicated a very good thermal stability of these samples up to the isotropization temperatures and over the whole temperature range of the liquid crystalline phase existence. Both complexes displayed a solid-state emission with quantum yields up to 8% at ambient temperature. The electrical properties of the new metallomesogens were investigated by variable temperature dielectric spectroscopy over the entire temperature range of the liquid crystalline phase. It was found that the liquid crystal phases favoured anhydrous proton conduction provided by the hydrogen-bonding networks formed by the NH…X moieties (X = halide or oxygen) of the benzoylthiourea ligand in the copper(I) complexes. A proton conductivity of 2.97 × 10-7 S·cm-1 was achieved at 430 K for the chloro-complex and 1.37 × 10-6 S·cm-1 at 440K for the related bromo-complex.

Schiff Bases Functionalized with T-Butyl Groups as Adequate Ligands to Extended Assembly of Cu(II) Helicates.

The study of the inherent factors that influence the isolation of one type of metallosupramolecular architecture over another is one of the main objectives in the field of Metallosupramolecular Chemistry. In this work, we report two new neutral copper(II) helicates, [Cu2(L1)2]·4CH3CN and [Cu2(L2)2]·CH3CN, obtained by means of an electrochemical methodology and derived from two Schiff-based strands functionalized with ortho and para-t-butyl groups on the aromatic surface. These small modifications let us explore the relationship between the ligand design and the structure of the extended metallosupramolecular architecture. The magnetic properties of the Cu(II) helicates were explored by Electron Paramagnetic Resonance (EPR) spectroscopy and Direct Current (DC) magnetic susceptibility measurements.

Quantum behaved artificial bee colony based conventional controller for optimum dispatch

&lt;p&gt;Since a multi area system (MAS) is characterized by momentary overshoot, undershoot and intolerable settling time so, neutral copper conductors are replaced by multilayer zigzag graphene nano ribbon (MLGNR) interconnects that are tremendously advantageous to copper interconnects for the future transmission line conductors necessitated for economic and emission dispatch (EED) of electric supply system giving rise to reduced overshoots and settling time and greenhouse effect as well. The recent work includes combinatorial algorithm involving proportional integral and derivative controller and heuristic swarm optimization; we say it as Hybrid- particle swarm optimization (PSO) controller. The modeling of two multi area systems meant for EED is carried out by controlling the conventional proportional integral and derivative (PID) controller regulated and monitored by quantum behaved artificial bee colony (ABC) optimization based PID (QABCOPID) controller in MATLAB/Simulink platform. After the modelling and simulation of QABCOPID controller it is realized that QABCOPID is better as compared to multi span double display (MM), neural network based PID (NNPID), multi objective constriction PSO (MOCPSO) and multi objective PSO (MOPSO). The real power generation fixed by QABCOPID controller is used to estimate the combined cost and emission objectives yielding optimal solution, minimum losses and maximum efficiency of transmission line.&lt;/p&gt;

Mononuclear copper(Ⅰ) complexes with mechanochromic thermally activated delayed fluorescence behaviour based on switchable hydrogen bonds

Four neutral mononuclear copper(I) complexes (1–4) with formula of [(N^P)Cu(PPh3)2] (1–2) and [(N^P)Cu(Xantphos)] (3–4) based on NH–deprotonated (2–(1H–benzimidazole)phenyl) diphenylphosphine ligands (N^P) and phosphine ancillary ligands have been synthesized. The copper(I) complexes exhibit bright thermally activated delayed fluorescence at room temperature with photoluminescence quantum yield up to 43.5%. Upon grinding, the complexes display apparent bathochromic shift in the emission maxima of up to 50 nm (1). Meanwhile, the complexes display similar luminescence profiles to those of the origin samples exposed to CH3OH vapor. Single crystal X–ray and PXRD diffraction results demonstrate that the reversible mechanochromic luminescent (MCL) properties are ascribed to the transformation of crystalline and amorphous state dependent on the disruption and restoration of hydrogen bonds during external stimuli, which have been rarely observed in the copper(I)-based MCL materials hitherto. These findings clearly suggest that the introduction of switchable secondary interactions in mononuclear copper(I) complex is a large-scale synthesis strategy for multifunctional luminescent materials.

Assessment of a thrust induced by a water-fueled magnetron sputtering source

Water-fueled low-pressure discharge is sustained by a magnetron sputtering source consisting of a copper cathode and a ring anode, and a force exerted to a target plate located downstream of the source is measured, where the water gas is continuously introduced by using a mass flow controller operational for a differential pressure lower than the water vaper pressure at a room temperature. The source and the dc power supply for the discharge are electrically floating from the grounded vacuum chamber to ensure zero net current between the source and the surroundings; the mass ejection of the sputtered and electrically neutral copper atoms or clusters are responsible for the thrust generation, while the ionized particles do not contribute to the thrust generation due to the plasma confinement near the cathode. The measurement shows the thrust generation of about 3–4 mN/kW at a discharge power level of about 80 W. The results would potentially lead a propulsion device with no neutralizer and no high-pressure gas storage tank.

Copper(II) Complexes of 5-Fluoro-Salicylaldehyde: Synthesis, Characterization, Antioxidant Properties, Interaction with DNA and Serum Albumins.

The synthesis, characterization and biological profile (antioxidant capacity, interaction with calf-thymus DNA and serum albumins) of five neutral copper(II) complexes of 5-fluoro-salicylaldehyde in the absence or presence of the N,N'-donor co-ligands 2,2'-bipyridylamine, 2,9-dimethyl-1,10-phenanthroline, 1,10-phenanthroline and 2,2'-bipyridine are presented herein. The compounds were characterized by physicochemical and spectroscopic techniques. The crystal structures of four complexes were determined by single-crystal X-ray crystallography. The ability of the complexes to scavenge 1,1-diphenyl-picrylhydrazyl and 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radicals and to reduce H2O2 was investigated in order to evaluate their antioxidant activity. The interaction of the compounds with calf-thymus DNA possibly takes place via intercalation as suggested by UV-vis spectroscopy and DNA-viscosity titration studies and via competitive studies with ethidium bromide. The affinity of the complexes with bovine and human serum albumins was examined by fluorescence emission spectroscopy revealing the tight and reversible binding of the complexes with the albumins.

Optoelectronic properties and ultrafast carrier dynamics of copper iodide thin films

As a promising high mobility p-type wide bandgap semiconductor, copper iodide has received increasing attention in recent years. However, the defect physics/evolution are still controversial, and particularly the ultrafast carrier and exciton dynamics in copper iodide has rarely been investigated. Here, we study these fundamental properties for copper iodide thin films by a synergistic approach employing a combination of analytical techniques. Steady-state photoluminescence spectra reveal that the emission at ~420 nm arises from the recombination of electrons with neutral copper vacancies. The photogenerated carrier density dependent ultrafast physical processes are elucidated with using the femtosecond transient absorption spectroscopy. Both the effects of hot-phonon bottleneck and the Auger heating significantly slow down the cooling rate of hot-carriers in the case of high excitation density. The effect of defects on the carrier recombination and the two-photon induced ultrafast carrier dynamics are also investigated. These findings are crucial to the optoelectronic applications of copper iodide.

Two Synthetic Approaches to Coinage Metal(I) Mesocates: Electrochemical versus Chemical Synthesis.

We report two different approaches to isolate neutral and cationic mesocate-type metallosupramolecular architectures derived from coinage monovalent ions. For this purpose, we use a thiocarbohydrazone ligand, H2L (1), conveniently tuned with bulky phosphine groups to stabilize the MI ions and prevent ligand crossing to achieve the selective formation of mesocates. The neutral complexes [Cu2(HL)2] (2), [Ag2(HL)2] (3), and [Au2(HL)2] (4) were prepared by an electrochemical method, while the cationic complexes [Cu2(H2L)2](PF6)2 (5), [Cu2(H2L)2](BF4)2 (6), [Ag2(H2L)2](PF6)2 (7), [Ag4(HL)2](NO3)2 (8), and [Au2(H2L)2]Cl2 (9) were obtained by using a metal salt as the precursor. All of the complexes are neutral or cationic dinuclear mesocates, except the silver nitrate derivative, which exhibits a tetranuclear cluster mesocate architecture. The crystal structures of the neutral and cationic copper(I), silver(I), and gold(I) complexes allow us to analyze the influence of synthetic methodology or the counterion role on both the micro- and macrostructures of the mesocates.

Cover Feature: Radical Complexes of Nickel(II)/Copper(II) and Redox Non‐innocent MB‐DIPY Ligands: Unusual Stability and Strong Near‐Infrared Absorption at λmax ∼1300 nm (Chem. Eur. J. 41/2022)

The preparation of radicals with intense and redox-switchable absorption beyond 1000 nm is a long-standing challenge in the chemistry of functional dyes. We now report a series of unprecedented stable neutral nickel(II) and copper(II) complexes of “Manitoba-dipyrromethenes” (MB-DIPYs) in which the organic chromophore is present in the anion–radical state. The new stable radicals have an intense absorption at λmax∼1300 nm and can be either oxidized to a regular [MII(MB-DIPY)]+ (M = Cu or Ni) or reduced to [MII(MB-DIPY)]− compounds. More information can be found in the Research Article by F. Thomas, J. van Lierop, V. N. Nemykin, and co-workers (DOI: 10.1002/chem.202201181).

Optical Investigation of Excited Species Distribution in Low-Current Vacuum Discharges

It is well-known that when high currents flow through a vacuum gap, anode spots are formed on the anode surface. However, anode flare phenomena are also observed in low-current vacuum discharges. The objective of this article is to experimentally observe the spatial distribution of excited Cu atoms and ions generated from a single cathode spot (CS) and to interpret the mechanism of the anode flare at low currents (40–80 A). Optical emission spectroscopy (OES) and laser-induced fluorescence (LIF) techniques have been used for investigating low-current vacuum arc discharge confined to axial magnetic fields (AMFs). The effects of AMFs and arc currents on the axial distribution of the radiation intensity were investigated for different copper ionization states (Cu I and Cu II). The highest luminance was found near the electrodes for both excited neutral copper atoms and ions, and only weak spectral lines of excited Ni atoms were detected in the near-anode region. With increasing the external AMF, a bright “spot” appeared near the anode surface. In the visible light range, excited atoms were the main contributor to anode flare in low-current vacuum discharge. As measured by LIF, the density of copper atoms near the anode increased from 10 <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\times 10^{17}$ </tex-math></inline-formula> to 14 <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\times 10^{17}\,\,\text{m}^{-3}$ </tex-math></inline-formula> when the applied magnetic fields increased from 31 to 74 mT. The anode flare contains far more excited atoms from the cathode material than the anode material. They are the results of cathodic plasma expansion to reach the anode after charge neutralization and reflection on the anode surface. For the single CS, the observed fact that a tiny number of atoms leave the anode surface and participate in the anode flare is more likely the result of a sputtering effect rather than thermal evaporation by cathode electron stream.

Radical Complexes of Nickel(II)/Copper(II) and Redox Non-innocent MB-DIPY Ligands: Unusual Stability and Strong Near-Infrared Absorption at λmax ∼1300 nm.

The preparation of radicals with intense and redox-switchable absorption beyond 1000 nm is a long-standing challenge in the chemistry of functional dyes. Here we report the preparation of a series of unprecedented stable neutral nickel(II) and copper(II) complexes of "Manitoba dipyrromethenes" (MB-DIPYs) in which the organic chromophore is present in the radical-anion state. The new stable radicals have an intense absorption at λmax ∼1300 nm and can be either oxidized to regular [MII (MB-DIPY)]+ (M=Cu or Ni) or reduced to [MII (MB-DIPY)]- compounds. The radical nature of the stable [MII (MB-DIPY)] complexes was confirmed by EPR spectroscopy with additional insight into their electronic structure obtained by UV-Vis spectroscopy, electro- and spectroelectrochemistry, magnetic measurements, and X-ray crystallography. The electronic structures and spectroscopic properties of the radical-based chromophores were also probed by density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. These nickel(II) and copper(II) complexes represent the first stable radical compounds with a MB-DIPY ligand.