CuI System Research Articles

Investigation of the electronic, optical, elastic, mechanical and vibrational properties of CuI using HSE03

Ab Initio density functional theory (DFT) simulations have been employed to systematically explore the electronic, optical, elastic, mechanical and vibrational properties. In this study, we revealed that [Formula: see text]-CuI has a wide direct bandgap energy of 3.21 eV, is pure covalent and brittle. We also found that the core level is made up of I s electron orbitals, the valence band is constructed with I p orbitals, and the Cu s orbital states mainly contribute to the conduction band minimum (CBM). The reflectivity of CuI is reported to be low (35.9% for the light reflected), showing high material absorption. A high absorption coefficient of [Formula: see text] is also reported. The elastic and mechanical properties can further confirm the mechanical stability of the CuI system, derived from DFT-calculated elastic constants and phonon dispersion from density functional perturbation theory (DFPT) calculations.

Robust quantum anomalous Hall effect in a pentagonal MoS2 monolayer grown on CuI(001) substrates

Recently, the square planar ${\mathrm{MoS}}_{2}$ monolayer, which exhibits the Cairo pentagonal tiling (termed as $1\mathrm{P}\text{\ensuremath{-}}{\mathrm{MoS}}_{2}$), was identified as an intrinsic quantum anomalous Hall (QAH) insulator. However, there is a paucity of theoretical work concerning a suitable substrate to support its nontrivial electron transport properties, which is the prerequisite for practical applications. Here. we demonstrate that CuI(001) serves an excellent substrate candidate for epitaxial growth of the $1\mathrm{P}\text{\ensuremath{-}}{\mathrm{MoS}}_{2}$ sheet by showing that the intrinsic ferromagnetism and the QAH state of $1\mathrm{P}\text{\ensuremath{-}}{\mathrm{MoS}}_{2}$ remain unaltered in the $1\mathrm{P}\text{\ensuremath{-}}{\mathrm{MoS}}_{2}$/CuI(001) system. Further analyses of the strain effect on $1\mathrm{P}\text{\ensuremath{-}}{\mathrm{MoS}}_{2}$ reveal that the QAH is robust within a strain range from $\ensuremath{-}$ 2% to 2%. Our findings will inspire the experimental realization of QAH effects in two-dimensional (2D) pentagon-based materials.

PHASE EQUILIBRIUMIN THE Cu2S – In2S3 – CuI QUASI-TERNARY SYSTEM

The interaction between the components in the Cu 2 S – In 2 S 3 – CuI system has been inverstigated by methods of X-ray analysis and differential-thermal analysis. An isothermal section of the quasi-ternary system at 770 K, two phase diagrams, three polythermal sections and the liquidus surface projection of the system were constructed. The isothermal section of the Cu 2 S – In 2 S 3 – CuI quasi-ternary system at 770 K has been built based on the results of the X-ray analysis. The large regions of the solid solutions based on binary, ternary and quaternary compounds do not form at 770 К. The following one-phase regions were fixedat the temperature: κ-solid solutions based on Cu 2 S with cubic structure (S.G. Fm -3 m ), η-solid solutions based on CuI (S. G. F -43 m ), e-solid solutions based on CuIn 2 S 3 I with a cubic structure (S. G. F -43 m ), δ′-solid solutions based on LTM-In2S3 (S.G. I -4/ amd ), μ-solid solutions based on CuIn 5 S 8 (S.G. Fd 3 m ), γ-solid solutions based on LTM-CuInS 2 (S.G. I -42 d ). These single-phase regions are separated by nine two-phase equilibria. The liquidus surface projection was built based on the two phase diagrams of In 2 S 3 –CuI and CuInS 2 – CuI systems and three polythermal sections CuIn 5 S 8 –CuIn 2 S 3 I, CuInS 2 –CuIn 2 S 3 I, CuInS 2 – “Cu 3 SI”, which have been constracted in this work. In addition, literature data about the interaction in In 2 S 3 – Cu 2 S and Cu 2 S – CuI systems have been used. The liquidus surface projection consists from the areas of primary crystallization of κ-solid solutions based on Cu 2 S, α-solid solutions based on HTM-CuInS 2 , β-solid solutions based on 2-HTM-CuInS 2 , γ-solid solutions based on LTM-CuInS 2 , μ-solid solutions based on CuIn 5 S 8 , δ-solid solutions based on HTM-In 2 S 3 , e-solid solutions based on CuIn 2 S 3 I, η-solid solutions based on CuI. These areas are separated by 18 mono-variant curves and 17 non-variant points.

Efficient synthesis, spectroscopic characterization and DFT based studies of novel 1-amide 4-sulfonamide-1,2,3-triazole derivatives

In the present study, for the first time 1-amide 4-sulfonamide-1,2,3-triazole scaffolds were synthesized by using an azide-alkyne Huisgen cycloaddition reaction. The target products were obtained in moderate to good yields (45–75%) by using catalytic CuI and green system H2O/EtOH. The easy availability of the inexpensive starting materials, avoiding isolation and handling of hazardous organic azides and mild reaction conditions make this method a valuable tool for generating functionalized 1,2,3-triazole derivatives. The unambiguous characterization of synthesized compounds was accomplished by using various spectroscopic techniques such as 1H NMR, 13C NMR, and FT-IR. The information regarding optimized geometry, were obtained by applying DFT/B3LYP-6-31G(d) method. The electrophilicity index, 1H and 13C chemical shift values, lithium and sodium ion affinities of the desired product 3b have been also calculated by the mentioned method. As a whole, the calculated results were found in close agreement to that of experimental data. The studies revealed that the compound 3b possesses good Li+ and Na+ affinity and cation π interaction plays a vital role in the complexation of 3b. For the first time, nucleus–independent chemical shift index was used to confirm the cation π interaction of 3b.

Development of a Large-Scale Copper(I)/TEMPO-Catalyzed Aerobic Alcohol Oxidation for the Synthesis of LSD1 Inhibitor GSK2879552

An improved process to an aldehyde en route to an LSD1 inhibitor was developed using an aerobic oxidation with a CuI and TEMPO (2,2,6,6-tetramethylpiperdine 1-oxyl) catalyst system. In this report, kinetic information is utilized to understand the generation a of number of key byproducts that affect catalyst performance and aldehyde yield. Insight into factors affecting the formation of these byproducts is presented. This CuI/TEMPO catalyst facilitates rapid conversion of the starting aliphatic alcohol in 1–2 h with apparent zero-order kinetics unprecedented for this substrate class with this catalyst system. Process optimization of catalyst components and reaction solvent led to the successful 400 g scale-up of this oxidation with bubbling air in a batch reactor.

Chalcogenide glass-ceramic with self-organized heterojunctions: application to photovoltaic solar cells

In this work, we present for the first time the concept of chalcogenide glass-ceramic for photovoltaic applications with the GeSe2–Sb2Se3–CuI system. It has been demonstrated that thin films, deposited with the sputtering technique, are amorphous and can be crystallized with appropriate heat treatment. The thin film glass-ceramic behaves as a p-type semiconductor, even if it contains p-type Cu2GeSe3and n-type Sb2Se3. The conductivity of Sb2Se3has been greatly improved by appropriate iodine doping. The first photovoltaic solar cells based on the association of iodine-doped Sb2Se3and the glass-ceramic thin films give a short-circuit current density JSCof 10 mA/cm2and an open-circuit voltage VOCof 255 mV, with a power conversion efficiency of about 0.9%.

The Synthesis and Electroluminescence Properties of 4-Benzofuranyl-1,8-Naphthalimide Derivatives

A series of fluorescence compounds, 4-benzofuranyl-1,8-naphthalimides, were prepared through cycloaddition reaction from 4-ethynyl-1,8-naphthalimides and o-iodophenols which catalyzed by a Pd(PPh3)2Cl2 / CuI system under mild conditions. The intermediate material, 4-ethynyl-1,8- naphthalimide, was synthesized from 4-bromo-1,8- naphthalimide and trimethylsilyl- acetylene. The absorption and fluorescence spectra of 4-benzofuranyl-1,8- naphthalimides were studied and the quantum yields were measured. The maximum UV/vis absorption spectra were in the range of 375-400 nm and the maximum emission spectra were in the range of 470-510 nm. The electro- luminescent properties were also mensurated through a doped electroluminescent device which contains 1% 1,8-naphthalimides and 99% CBP (4,4'-N,N'-dicarbazole-biphenyl), It’s shown the maximum brightness reached 3700 cd/ m2 at 22.5V.

Copper mediated defluorinative allylic alkylation of difluorohomoallyl alcohol derivatives directed to an efficient synthetic method for ( Z)-fluoroalkene dipeptide isosteres

Difluoroallylation of optically pure O-silylated ( S)-2-methyl-3-hydroxypropanal 10a with bromodifluoropropene mediated by indium provided the corresponding difluorohomoallyl alcohol 11a with low diastereoselectivity, but without a decrease in optical purity. Defluorinative allylic alkylation of each diastereomer of the difluorohomoallyl alcohol efficiently proceeded by the reaction with trialkylaluminium and Cu(I) system or Grignard reagent and a catalytic amount of CuI system in THF to give the fluorine-substituted allylic alcohol 12 in an high yield and in an excellent Z selective manner. Subsequent imidate Claisen rearrangement of the allylic alcohol 12 proceeded with a complete 1,3-chirality transfer to give the fluoroalkene dipeptide isostere structure 14 after the final conversion of the primary alcohol 20 into the carboxylic acid form.

Synthesis and Structure of Four‐Coordinate Copper(II) Complexes Stabilized by β‐Ketiminato Ligands and Application in the Reverse Atom‐Transfer Radical Polymerization of Styrene

AbstractThe reaction of CuCl2 with R2NCH2CH2NHC(Me)=CHCO(Me) [R = Me (HL1) or Et (HL2)] in the presence of Et3N leads to the formation of complexes [CuCl(Ln)] [n = 1 (1), 2 (2)]. Whereas the solid‐state structure of compound 2 is mononuclear with a close to square‐planar arrangement of the ClON2 donor set, compound 1 adopts a dinuclear di‐μ‐chlorido arrangement in which two mononuclear units having essentially the same arrangement as in 2 establish loose axial Cu···Cl interactions, each one of them with the Cl atom of the other one. Compounds 1 and 2 have been tested as reversible trapping agents for the controlled radical polymerization of styrene under a reverse atom‐transfer radical polymerization (ATRP) approach. Reversible Cl atom transfer leading to a controlled polymerization process is observed, although the controllability is negatively affected by slow radical trapping. A moderate effect on the polymerization rate, once all the radical initiator is consumed, was observed in the presence of an excess amount of pyridine (10 equiv. per Cu) and interpreted on the basis of the stabilization of the CuI system.

ChemInform Abstract: Homocoupling Reaction of Terminal Alkynes Catalyzed by a Reusable Cationic 2,2′‐Bipyridyl Palladium(II)/CuI System in Water.

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The structure of molten CuCl, CuI and their mixtures as investigated by using neutrondiffraction

The structure of molten CuCl, CuI and their mixtures(CuCl)x(CuI)1−x with x = 0.294, 0.576, 0.801 was studied by using neutron diffraction. The results are discussed byreference to the information that is available on the structure of CuCl and CuI fromexperiment, theory and computer simulation. The comparison points to a need for morerealistic models for the CuCl–CuI system which should take into account the presence ofchemical bonds that have been found in CuI by the application of ab initio moleculardynamics methods.

Homocoupling reaction of terminal alkynes catalyzed by a reusable cationic 2,2′-bipyridyl palladium(II)/CuI system in water

A cationic 2,2′-bipyridyl palladium(II)/CuI system was proven to be a reusable and highly efficient catalyst for the homocoupling of terminal alkynes at room temperature using water as a solvent in the presence of TBAB under aerobic conditions. For aromatic terminal alkynes, the reaction was performed either with or without I2 as an oxidant; the addition of I2 was required when aliphatic terminal alkynes were used as a substrate for the homocoupling reaction. In the presence of 0.0001–1 mol% palladium catalyst and 1 mol% CuI, a variety of terminal alkynes were homocoupled in good to excellent yields. The water-soluble catalytic system was separated from the organic products by extraction and the residual aqueous solution showed activity for reuse for several cycles without a significant decrease in activity.

Metal specificity in DNA damage prevention by sulfur antioxidants

Metals such as CuI and FeII generate hydroxyl radical (OH) by reducing endogenous hydrogen peroxide (H2O2). Because antioxidants can ameliorate metal-mediated oxidative damage, we have quantified the ability of glutathione, a primary intracellular antioxidant, and other biological sulfur-containing compounds to inhibit metal-mediated DNA damage caused hydroxyl radical. In the CuI/H2O2 system, six sulfur compounds, including both reduced and oxidized glutathione, inhibited DNA damage with IC50 values ranging from 3.4 to 12.4μM. Glutathione and 3-carboxypropyl disulfide also demonstrated significant antioxidant activity with FeII and H2O2. Additional gel electrophoresis and UV–vis spectroscopy studies confirm that antioxidant activity for sulfur compounds in the CuI system is attributed to metal coordination, a previously unexplored mechanism. The antioxidant mechanism for sulfur compounds in the FeII system, however, is unlike that of CuI. Our results demonstrate that glutathione and other sulfur compounds are potent antioxidants capable of preventing metal-mediated oxidative DNA damage at well below their biological concentrations. This novel metal-binding antioxidant mechanism may play a significant role in the antioxidant behavior of these sulfur compounds and help refine understanding of glutathione function in vivo.

A Convenient Preparation of 5-Iodo-1,4-disubstituted-1,2,3-triazole: Multicomponent One-Pot Reaction of Azide and Alkyne Mediated by CuI−NBS

The system of CuI and NBS was found to provide both I (+) and Cu (+) for the first time. An efficient method for preparation of 5-iodo-1,4-disubstituted-1,2,3-triazole was achieved by multicomponent one-pot reaction of azides with alkynes in the presence of the novel CuI and NBS catalytic system. The high tolerance of various sensitive groups revealed the potential applications of this method in organic synthesis and drug discovery.

Ionic Conductivity and Phase Transition Behaviour in 4AgI‐(1‐x)PbI2‐2xCuI System

Samples of general formula 4AgI‐(1‐x)PbI2‐2xCuI, x = 0–0.4, have been prepared and investigated by XRD, DSC, and temperature‐dependent conductivity studies. X‐ray diffractograms showed the presence of binary system consisting of AgI and PbI2 in the sample x = 0. Cu‐substituted samples showed very similar diffractograms to that of the pure compound which indicates that no effect for the substitution on the nature of the binary system. DSC curves showed the presence of phase transition whose temperature increased with Cu+ ratio in the system. Ionic conductivity measurements confirmed the occurrence of the phase transition and showed that the high temperature phase is superionic conducting, whose conductivity increases with the increasing Cu+ amount in the system.

High temperature XRD studies of nanoscale AgI–CuI solid solutions

A preliminary high-temperature X-ray diffraction (HT-XRD) study of the nanometer-sized solid solution phases in the AgI–CuI system is reported through an extended range of temperatures (300–723K) covering phase transitions in both AgI and CuI. A major feature of this work is the observation of the coexistence of the zincblende and base-centred cubic phases of AgI over an extended range of temperatures the temperature width being a function of Cu content in the binary. The lattice parameters derived from HT-XRD data reflect systematics of phase transitions with progressive Cu substitution of AgI. The present results are discussed together with our earlier ionic conductivity, dilatometry and DSC data which have helped deduce phase diagrams for both the Ag-rich and Cu-rich regions of the binary.

Search for a novel zero thermal expansion material: dilatometry of the AgI-CuI system

AgI is a well-known superionic conductor possessing a negative thermal expansion (NTE) coefficient while CuI is a p-type semiconductor possessing a positive thermal expansion coefficient. Pellets of X-Ray Diffraction (XRD) characterized compositions in the AgI–CuI system namely, β AgI, γ AgI, Ag0.5Cu0.5I, Ag0.25Cu0.75I, Ag0.10Cu0.90I, Ag0.05Cu0.95I and γ CuI have been examined by quartz pushrod dilatometry measurements in order to look for a zero thermal expansion material. It is found that the systematic displacement of Ag by Cu gradually reduces the NTE anomaly in AgI. The composition Ag0.25Cu0.75I apparently exhibits near-zero thermal expansion. The results are discussed qualitatively in terms of relevant models.

A Facile Method for Synthesis of Alkyl Phenyl Selenides. The Reaction of Diphenyl Diselenide with Oxygen‐Containing Compounds Using La/Me3SiCl/cat.I2/cat.CuI System.

AbstractFor Abstract see ChemInform Abstract in Full Text.

A Facile Method for Synthesis of Alkyl Phenyl Selenides. The Reaction of Diphenyl Diselenide with Oxygen-containing Compounds Using La/Me3SiCl/cat.I2/cat.CuI System

Abstract Alcohols, ethers, and esters were directly converted to the corresponding alkyl phenyl selenides by the reaction of diphenyl diselenide and the La/Me3SiCl/cat.I2/cat.CuI. It was suggested that alkyl phenyl selenides were formed by the SH2 type reaction of diphenyl diselenide with alkyl radicals generated from alcohols, ethers or esters.

Deoxygenative Dimerization of Benzylic and Allylic Alcohols, and Their Ethers and Esters Using Lanthanum Metal and Chlorotrimethylsilane in the Presence of a Catalytic Amount of Iodine and Copper(I) Iodide.

AbstractFor Abstract see ChemInform Abstract in Full Text.