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.
Wojakowska, A.,Konieczna, E.
, p. 955 - 960 (1995)
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.
Hikmet, I.,Dufour, C.,Pinchemel, B.
, p. 147 - 152 (1993)
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.
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.
Synthesis and characterizations of nanoribbons and monodispersed nanocrystals of CuBr
Yang, Ming,Zhu, Jun-Jie
, p. 265 - 270 (2005)
Nanoribbons and monodispersed nanocrystals of CuBr have been prepared by a simple reaction between CuO suspension, NH2OH·HCl and KBr in the presence of deionized gelatin at 10°C. The products were characterized by X-ray powder diffraction, transmission electron microscopy and UV-vis absorption spectroscopy. The sizes of the monodispersed nanocrystals of CuBr were estimated by Debye-Scherrer formula according to XRD spectrum.
Carr, N. J.,Galwey, A. K.,Mohamed, M. A.
, p. 323 - 334 (1986)
Two anionic [CuI6X7]nn- (X=Br and I) chain-based organic-inorganic hybrid solids with N-substituted benzotriazole ligands
Gao, Xia,Zhai, Quan-Guo,Li, Shu-Ni,Xia, Rui,Xiang, Hai-Juan,Jiang, Yu-Cheng,Hu, Man-Cheng
, p. 1150 - 1158 (2010)
Solvothermal reactions of the flexible ligand 1,6-Bi(benzotriazole)hexane with CuI and KI or CuBr and KBr in ethanol generate two hybrid compounds, namely, {(HETA)[(Cu6I7)(ETA)2]}n(1) and {K(Cu6Br7)(BBTH)}n(2) (ETA=N-ethylbenzotriazole, HETA=protonated N-ethylbenzotriazole, BBTH=1,6-bi(benzotriazole)hexane). In 1, two [Cu3I4] vertex missing cubane-like subunits link each other by sharing one I atom to give a [Cu6I7] cluster, which further form novel 1D [Cu6I7]nn- anionic chain. Two in-situ generated ETA ligands finished the 4-coordinated environments of copper centers and another one discrete protonated ETA ligand keeps the charge neutrality for 1. In complex 2, bowl-shaped [Cu5Br4] clusters and rhomboid [Cu2Br2] dimers link each other to generate a [Cu6Br7]nn- 1D chain. BBTH ligands complete the tetrahedral spheres of Cu(I), and 7-coordinated K atoms further extend the 1D chain motifs to a 2D hybrid layer of 2. The UV-vis diffuse reflectance spectrum and luminescence measurements show that compound 1 and 2 both are potential semiconductor and photoluminescence materials.
Wojakowska, A.
, p. 91 - 98 (1989)
Molecular metals based on copper(II) 2,9,16,23-tetrahalo substituted phthalocyanine derivatives
Achar,Jayasree
, p. 719 - 733 (2000)
Pure copper(II) 2,9,16,23-symmetrically tetrahalo substituted phthalocyanine complexes, CuPTX (where X = F, Cl, Br and I) were synthesized. Elemental analyses, electronic, IR, magnetic susceptibility measurements, ESR, X-ray diffraction and TGA studies were carried out on the above complexes both before and after iodine doping, to characterize and investigate the effect of substituents as well as the iodine doping on the electrical properties of the copper phthalocyanine complexes. Variations in the electrical conductivity of the complexes depend on the nature of the substituents and were found to show ～105 times improved electrical conductivity in comparison to the parent phthalocyanine. It is interesting to note that substitution and iodine doping showed remarkably increased electrical conductivity, nearly 1012 times the electrical conductivity of copper phthalocyanine. This may be due to a decrease in the metal-metal bond distance, increase in the approach of an ideal eclipsed system or due to the combined effects of both.
Continuous and green microflow synthesis of azobenzene compounds catalyzed by consecutively prepared tetrahedron CuBr
Qin, Hong,Liu, Chengkou,Lv, Niuniu,He, Wei,Meng, Jingjing,Fang, Zheng,Guo, Kai
, (2019/12/24)
An environmentally friendly and cross-selective process intensification for the continuous synthesis of symmetric aromatic azo compounds by using self-made cuprous bromide as the catalyst under mild conditions in the microreactor was developed. A novel tetrahedron cuprous bromide catalyst which shows outstanding catalytic activity and satisfactory stability has been synthesized in continuous flow microreactor. The online immobilization of self-made cuprous bromide on the catalyst bed achieved oxidative coupling of aromatic amines (oxygen as oxidant) and high-performance gas–liquid–solid three-phase reaction, which strongly limited the possibility of undesired reaction pathways, improving product selectivity and reducing waste generation. Meanwhile, the yield of azo-coupling reaction was up to 98% under optimized condition. As compared with earlier traditional method (diazotization reaction) for synthesizing azobenzene, the designed micro-flow process displays signi?cant advances in terms of selectivity, waste emissions, sustainability and productivity. The combination of online immobilization of self-made cuprous bromide and precise and safe control through the microreactor provides a green solution for the industrial production of valuable aromatic azo compounds.
Synthesis, structures, antimicrobial activity and biosafety evaluation of pyridine-2-formaldehyde-N-susbtituted-thiosemicarbazonates of copper(ii)
Kaushal, Mani,Lobana, Tarlok S.,Nim, Lovedeep,Kaur, Jaskamal,Bala, Ritu,Hundal, Geeta,Arora, Daljit S.,Garcia-Santos, Isabel,Duff, Courtney E.,Jasinski, Jerry P.
, p. 15879 - 15894 (2018/10/04)
Pyridine-2-formaldehyde-N1-substituted-thiosemicarbazones {(C5H4N4)HC2═N3-N2(H)-C1═(S)N1HR} (abbrev. HL1-R: R = Me, Et, Ph) with copper(i) halides in an acetonitrile-dichloromethane mixture (1?:?1, v/v) have yielded a novel series of CuII complexes with a central coordination core: [CuIIX(N,N,S-L1-R)] (R = Me, Et, Ph: X = I, 1-3; Br, 4-6, Cl, 7-9), which have been characterized with the help of analytical data, IR, UV-visible and ESR spectroscopy, ESI-mass spectrometry and single crystal X-ray crystallography. The thio-ligands coordinate to CuII as anions (L1-R)? through pyridyl nitrogen-N4, azomethine nitrogen-N3 and thiolato sulfur and CuII is further bonded to iodide, bromide or chloride. In order to explore their bio-activity, complexes (1-9) as well as the previously reported CuII complexes of 2-benzoylpyridine-N-substituted thiosemicarbazones {(C5H4N4)(C6H5)-C2═N3-N2(H)-C1═(S)-N1HR; HL2-R}, namely, [CuIIX(N,N,S-L2-R)] (R = Me, Et, Ph: X = I, 10-12; Br, 13-15; Cl, 16-18), have been evaluated for their antimicrobial potential against different microbial strains. The microbial strains investigated are Staphylococcus aureus (MTCC740), Klebsiella pneumoniae (MTCC530), Shigella flexneri (MTCC1457), Salmonella typhimurium 1 (MTCC98), Salmonella typhimurium 2 (MTCC1251), Escherichia coli (MTCC119), Staphylococcus epidermidis (MTCC435), methicillin resistant Staphylococcus aureus (MRSA) and a yeast culture Candida albicans (MTCC227). Several complexes tested have shown high antimicrobial activity; specifically, against methicillin resistant Staphylococcus aureus, Staphylococcus epidermidis and Salmonella typhimurium 2; the activity is found to be high at low minimum inhibitory concentration (MIC) values as compared to that of the standard Gentamicin. Using MTT cytotoxicity assay {MTT = 3-[(4,5-dimethylthiazol-2-yl)-2,5-diphenyl]tetrazolium bromide}, complexes tested were found to be biosafe with high cell viability (90-98%).
