7787-70-4Relevant articles and documents
Quasi-2D Heisenberg Antiferromagnets [CuX(pyz)2](BF4) with X = Cl and Br
Kubus, Mariusz,Lanza, Arianna,Scatena, Rebecca,Dos Santos, Leonardo H. R.,Wehinger, Bj?rn,Casati, Nicola,Fiolka, Christoph,Keller, Lukas,Macchi, Piero,Rüegg, Christian,Kr?mer, Karl W.
, p. 4934 - 4943 (2018)
Two Cu2+ coordination polymers [CuCl(pyz)2](BF4) 1 and [CuBr(pyz)2](BF4) 2 (pyz = pyrazine) were synthesized in the family of quasi two-dimensional (2D) [Cu(pyz)2]2+ magnetic networks. The layer connectivity by monatomic halide ligands results in significantly shorter interlayer distances. Structures were determined by single-crystal X-ray diffraction. Temperature-dependent X-ray diffraction of 1 revealed rigid [Cu(pyz)2]2+ layers that do not expand between 5 K and room temperature, whereas the expansion along the c-axis amounts to 2%. The magnetic susceptibility of 1 and 2 shows a broad maximum at ～8 K, indicating antiferromagnetic interactions within the [Cu(pyz)2]2+ layers. 2D Heisenberg model fits result in J∥ = 9.4(1) K for 1 and 8.9(1) K for 2. The interlayer coupling is much weaker with |J⊥| = 0.31(6) K for 1 and 0.52(9) K for 2. The electron density, experimentally determined and calculated by density functional theory, confirms the location of the singly occupied orbital (the magnetic orbital) in the tetragonal plane. The analysis of the spin density reveals a mainly σ-type exchange through pyrazine. Kinks in the magnetic susceptibility indicate the onset of long-range three-dimensional magnetic order below 4 K. The magnetic structures were determined by neutron diffraction. Magnetic Bragg peaks occur below TN = 3.9(1) K for 1 and 3.8(1) K for 2. The magnetic unit cell is doubled along the c-axis (k = 0, 0, 0.5). The ordered magnetic moments are located in the tetragonal plane and amount to 0.76(8) μB/Cu2+ for 1 and 0.6(1) μB/Cu2+ for 2 at 1.5 K. The moments are coupled antiferromagnetically both in the ab plane and along the c-axis. The Cu2+ g-tensor was determined from electron spin resonance spectra as gx = 2.060(1), gz = 2.275(1) for 1 and gx = 2.057(1), gz = 2.272(1) for 2 at room temperature.
GALVANOSTATIC PULSE PLATING OF COPPER AND COPPER (I) HALIDES FROM ACID COPPER (II) HALIDE SOLUTIONS.
Yeow,Hibbert
, p. 786 - 790 (1983)
CuX (X equals Cl or Br) is formed during the galvanostatic pulse plating of copper from acid solutions containing Cu**2** plus and X** minus . The reaction Cu**2** plus plus Cu degree plus 2X** minus yields 2CuX occurs in the relaxation period of the puls
Beyond Classical Coordination Chemistry: The First Case of a Triply Bridging Phosphine Ligand
Baranov, Andrey Y.,Pritchina, Elena A.,Berezin, Alexey S.,Samsonenko, Denis G.,Fedin, Vladimir P.,Belogorlova, Nataliya A.,Gritsan, Nina P.,Artem'ev, Alexander V.
, p. 12577 - 12584 (2021)
The first example of a triply bridging (μ3-P) phosphine ligand has been discovered in the crown-shaped [Cu3(μ2-Hal)3L] (Hal=Cl, Br, or I) complexes supported by tris[2-(2-pyridyl)ethyl]phosphine (L). Theoretical analysis completely confirms the observed μ3-P-bridging pattern, revealing the interaction of the same lone pair of phosphorus with three valence 4s-orbitals of Cu atoms. The presented complexes exhibit outstanding blue phosphorescence (λem=442–465 nm) with the quantum efficiency reaching 100 %. The complex [Cu3(μ2-I)3L] also exhibits remarkable thermo- and mechanochromic luminescence resulting in a sharp change in the emission colour upon external stimuli. These findings essentially contribute to coordination chemistry of the pnictine ligands.
Synthesis, crystal structure and properties of CuBr(2,3-dimethylpyrazine) coordination polymers
Je?, Inke,Taborsky, Petr,N?ther, Christian
, p. 501 - 507 (2007)
Reaction of CuBr with an excess of 2,3-dimethylpyrazine in acetonitrile leads to the formation of the literature known ligand-rich 1:1 compound poly[μ2-bromo-μ2-2,3-dimethylpyrazine-N, N′-copper(I)] (1). On heating this compound in a thermobalance a transformation into the new ligand-deficient 2 :1 compound poly[di- μ3-bromo-μ2-2,3-dimethylpyrazine-N, N′-dicopper(I)] (3) is observed, which later was also prepared in solution. This compound crystallizes in the monoclinic space group P2 1/n with all atoms in general positions. In the crystal structure the Cu atoms are surrounded by three Br atoms and one 2,3-dimethylpyrazine ligand within a distorted tetrahedron. The tetrahedra are connected via common Br edges into CuBr double chains, which are connected by the ligands into layers located in the ab plane. The formation of compounds 1 and 3 was also investigated in solution. The results have shown that compound 1 can only be prepared if an excess of the ligand is used. If CuBr and the ligand are reacted in a ratio of 1 : 1, in the beginning the literature known ligand-deficient 3 : 2 intermediate catena[tribromo-μ2-bis(μ2-2,3-dimethylpyrazine-N, N′)-tricopper(I)] (2) is obtained, which transforms within minutes into compound 3. If a crystalline suspension of compound 1 is stirred in acetonitrile a transformation into the most stable compound 3 is also observed. The luminescence properties of compounds 1 and 3 were investigated. The complexes show differences mainly in the emission spectra.
Electrical conductivity of CuSn5Br11 in solid and molten states
Wojakowska,Kundys
, p. 3780 - 3784 (1990)
The electrical conductivity of solid and molten CuSn5Br11 and SnBr2 compounds was determined using classical a.c. bridge techniques and sealed capillary-type cells with platinum electrodes. The solid compound CuSn5Br11 may be a fast Cu+ ion conductor. The specific conductance of the molten compound is nearly the same as that of the molten stannous bromide. Its conduction is mostly due to motion of the anions.
A thermoanalytical study of copper(I) thiocarbamide compounds
Krunks,Leskelae,Mutikainen,Niinistoe
, p. 479 - 484 (1999)
Hydrated isostructural 1:3 complexes of copper(I) chloride and bromide with thiourea were synthesised and their thermal decomposition studied by simultaneous TG/DTA complemented by ex situ FTIR and XRD studies. The decomposition of Cu(tu)3Cl·H2O is initiated by dehydration around 100°C, followed by a total multi-step degradation of the structure in the temperature range of 200-600°C. The counter ion has some influence on the temperatures and composition of the solid residue. The results were compared with those obtained with the 1:1 complex Cu(tu)Cl 1/2H2O.
New Cu(i) halide complexes showing TADF combined with room temperature phosphorescence: The balance tuned by halogens
Artem'Ev, Alexander V.,Baranov, Andrey Yu.,Berezin, Alexey S.,Kolesnikov, Ilya E.,Mazur, Anton S.,Plyusnin, Viktor F.,Samsonenko, Denis G.,Tolstoy, Peter M.
, p. 3155 - 3163 (2020)
A series of Cu(i) halide complexes derived from tris(2-pyridyl)phosphine (Py3P), [Cu2(Py3P)2X2] (X = Cl, Br, I), have been synthesized by a straightforward reaction in solution or through a mechanochemical route. At room temperature, the solid complexes exhibit bright dual-mode photoluminescence (λmax = 520-550 nm, τ = 14.5-20.0 μs, and ΦPL ≈ 53%), expressed by thermally activated delayed fluorescence (TADF) combined with phosphorescence (PH), originating from 1(M + X)LCT and 3(M + X)LCT excited states, respectively. Remarkably, the balance of these radiative processes at 300 K is regulated by halogen atom nature, switching from TADF-assisted phosphorescence to PH-admixed TADF. The emission of [Cu2(Py3P)2Cl2] at 300 K is largely contributed by PH (73%) admixed with the TADF fraction (27%) and [Cu2(Py3P)2Br2] also emits mainly PH (65%) admixed with the larger TADF fraction (35%). Meanwhile, for [Cu2(Py3P)2I2], the TADF channel becomes dominating (61%) and PH contribution drops to 39%. The photophysical study corroborated by (TD)DFT computations has revealed that this effect arises mainly from the narrowing of the ΔE(S1 - T1) gap of the [Cu2(Py3P)2X2] complexes in the order Cl (1500 cm-1) > Br (1250 cm-1) > I (1000 cm-1) which facilitates the TADF pathway and suppresses PH in the same order.
Two enantiomers of [Cu3(mnt)3]3- as ligands to Cu(i) or Ag(i) in building [Cu6M2(mnt) 6]4- complexes (M = Cu or Ag) with the reversal of the reaction by X- (X = Cl, Br)
Maiti, Biplab K.,Pal, Kuntal,Sarkar, Sabyasachi
, p. 1003 - 1008 (2008)
Two enantiomers of [Bu4N]3[Cu3(mnt) 3] (1) formed by Na2(mnt) (mnt = maleonitriledithiolate, [S2C2(CN)2]2-) and CuCl in a 11 molar ratio react further with MCl (M = Cu or Ag) involving both the enantiomers of 1 to produce the larger complex, [Bu4N]4[Cu 6M2(mnt)6] (M = Cu (2), Ag (3)) from which the capped Cu+ or Ag+ ion can readily be removed by Bu 4NX (X = Cl, Br), reverting 2 or 3 back to 1. Such reversal does not work with non-coordinating anions like BF4-, ClO 4- and PF6-. The Royal Society of Chemistry.
On the oximine complexes of transition metals. 106. Spectroscopic and DSC study of some complexes of the types [Cu(DioxH)2] and [CuX2·DioxH2]
Zsako,Nagy,Varhelyi,Novak,Lovasz
, p. 421 - 429 (1998)
Several new complexes of the types [Cu(DioxH)2] and [CuX2·DioxH2] (DioxH2: aliphatic or alicyclic α-dioxime) were obtained and characterized by means of near and far Fourier transformation IR spectroscopy. The t
Crystal Structure of High Temperature Phase and Ionic Conductivity Mechanism of CuHgSX (X = Cl, Br)
Moro'oka, Masakazu,Ohki, Hiroshi,Yamada, Koji,Okuda, Tsutomu
, p. 2111 - 2115 (2003)
We found a new ionic conduction phase in CuHgSCl above 373 K and in CuHgSBr above 346 K. The crystal structures of these novel phases have been determined by Rietveld refinement of powder X-ray diffraction patterns. The electric conductivity at 500 K measured by AC impedance method was 1.4 × 10-5 S cm-1 for CuHgSCl and 4.0 × 10-6 S cm-1 for CuHgSBr. The activation enthalpy was determined to be 53 kJ mol-1 for CuHgSCl and 67 kJ mol-1 for CuHgSBr. The ionic transport number measurements indicated that Cu+ ions constitute the majority charge carriers in these samples. The electronic contribution to the conduction process is small in comparison with the Cu+ ionic contribution. The charge density analysis by the maximum entropy method (MEM) combined with Rietveld analysis clearly showed that the Cu+ ionic conduction path was along the crystallographic (100) direction.
