Fig 3 - uploaded by Marina Roxburgh
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![(top) Positive ion electrospray mass spectrum showing the isotope pattern of the freshly prepared red solution in MeOH, showing the peak at m/z assigned to [(L 23 ) 2 Cu(I)] +. (bottom) Isotope pattern of the aged olive green solution in MeOH showing the peak at m/z assigned to [(L 23 )(L 23-H)Cu(II)] +. Insets show calculated isotope pattern for each of the copper species.](profile/Marina-Roxburgh-2/publication/271380420/figure/fig2/AS:493060875395073@1494566281723/top-Positive-ion-electrospray-mass-spectrum-showing-the-isotope-pattern-of-the-freshly.png)
(top) Positive ion electrospray mass spectrum showing the isotope pattern of the freshly prepared red solution in MeOH, showing the peak at m/z assigned to [(L 23 ) 2 Cu(I)] +. (bottom) Isotope pattern of the aged olive green solution in MeOH showing the peak at m/z assigned to [(L 23 )(L 23-H)Cu(II)] +. Insets show calculated isotope pattern for each of the copper species.
Source publication
Five complexes prepared from CuI and dipyridyl ketone oxime ligands were synthesised and structurally characterised, [Cu2I2(L23)(L23-H)]∞, 1, [Cu(L23-H)2]∞, 2, {[Cu2(L24)(L24-H)I2](CH3CN)}∞, 3, [Cu(L33)I]∞, 4, and {[Cu8(L44)5I8](CH3CN)4(C4H10O)2(H2O)2}∞, 5. The effect of the varying pyridyl substitution patterns of L23, L24, L33 and L44 was investi...
Context in source publication
Context 1
... out under normal operating conditions. The spectra showed a subtle change as the sample aged. The red solution showed a peak at 461 m/z which was assigned as [(L 23 ) 2 Cu(I)] + . The olive green solu- tion showed a peak at 460 m/z which was assigned as [(L 23 )(L 23 -H)Cu(II)] + . Thus, over time it appeared that the Cu(I) ion was being oxidized (Fig. ...
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Citations
... Therefore, it is very interesting to develop novel xanthate ester surfactants with double chelating groups as flotation collectors. Oxime, a unique family with the molecular formula of RR'C = N -OH, can act as chelating agents with various metal ions, including Cu, Ag, Ni, Pt, Co, Rh and Mn [15][16][17][18][19][20][21] . Hoły ńska [18] concluded that cupric ions coordinated with phenyl 2-pyridyl ketoxime through its oxime N and O atoms to form Cu -N -O -Cu bridge. ...
In this paper, a novel surfactant, O-isopropyl-S-[2-(hydroxyimino) propyl] dithiocarbonate ester (IPXPO) was synthesized and first introduced as a collector, and its flotation behavior and adsorption mechanism to chalcopyrite were investigated by micro-flotation, adsorption thermodynamics and kinetics, in situ scanning electrochemical microscopy (SECM), Zeta potential and FTIR spectroscopy. IPXPO exhibited superior flotation performances to chalcopyrite in comparison to pyrite and preferably attached on to chalcopyrite surfaces at pH 4–9. The adsorption IPXPO on to chalcopyrite was agreed well with Langmuir isotherm and pseudo-second-order equation, and the adsorption ΔH (enthalpy change), ΔS (entropy change), ΔG (free energy change) and Ea (activation energy) were 70.44 kJ/mol, 332.23 J/mol/K, −28.49 kJ/mol (298 K) and 22.85 kJ/mol respectively, inferring a spontaneously endothermic chemisorption process. Zeta potential and in situ SECM images demonstrated that IPXPO might anchor on the positively charged sites of chalcopyrite surface to form new species. FTIR spectra further elucidated that the IPXPOCu surface complexes were produced probably by reaction of CS and CNOH groups of IPXPO with copper atoms to form CuS, CuN and CuO bonds on chalcopyrite surfaces. IPXPO's unique properties, such as two chelating groups and characteristic adsorption manner, rendered it to be a good collector for chalcopyrite flotation.
... Previous structures (2) with CuI and the ligand 2,3-dipyridyl ketone oxime (L 23 ) showed a mixed valence polymer was formed in which the Cu(II) ion was stabilised by the formation of a pseudo-tetradentate oxime-oximato bridge. It was of interest to investigate how L 23 could be more generally used to generate other Cu(II) coordination polymers given that alongside these attractive binding features it also has the ability to deprotonate at the oxime giving either the oximato, pseudo-tetradentate oxime-oximato or rare zwitterionic form of the ligand. ...
... The orientation of the two L 23 entities formed a bridged intramolecular oxime-oximato hydrogen bond (2). The O-H⋯O distances were found to be 1.18(3) and 1.28(3) Å, respectively, (corresponding to an O···O distance of 2.447(3) Å) with the hydrogen being shared roughly equally between the two oxygen atoms, reflecting the strong oxime-oximato bridge. ...
... The two L 23 entities were bound together in a bridged intramolecular oxime-oximato hydrogen bond (2). The O-H⋯O distances were found to be 1.15(3) and 1.31(3) Å, respectively, (corresponding to an O···O distance of 2.450(4) Å). ...
Four new compounds prepared from the ligand 2,3-dipyridyl ketone oxime (L23) with varying Cu(II) salts were synthesised and structurally characterised, {[Cu(L23)(L23-H)](ClO4)}∞ (1), {[Cu(L23)(L23-H)](BF4)1/4(H2O)}∞ (2), [Cu3(L23-H)2(L23′)(NO3)2OH]2(NO3)2(C3H8O)6 (3) and [Cu(L23)Cl2]∞ (4). The effects of differing counterions, as well as the rotational conformational versatility of L23, were demonstrated by the differing polymeric structures that were observed. Complex 1 and 2 both existed as 1-D polymeric chains with L23 acting as a pseudo-tetradentate ligand through an oxime-oximato bridge. Complex 1 formed a helical arrangement while 2 formed a chiral chain with both 1 and 2 exhibiting similar chiral packing. Complex 3 formed an unusual inverse-9-metallacrown-3 complex, with one of the L23 ligands in a zwitterionic form. Complex 4 was present as a simple 1-D meso-helical chain.
The adsorption mechanism of O-isopropyl-S- [2- (hydroxyimino) propyl] dithiocarbonate ester (IPXPO) to chalcopyrite was investigated by using contact angle, in-situ atomic force microscopy (in-situ AFM), cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS). The results of contact angle and in-situ AFM demonstrated that IPXPO adsorbed on chalcopyrite increases surface hydrophobicity and roughness. It was found by CV experiments that a layer passive film was formed. The results of XPS spectra further revealed that the thiol S atom, oxime N atom, and O atom in the IPXPO molecule might react with copper atoms to form Cu-S, Cu-N, and Cu-O bonds, respectively. An artificial mixed minerals flotation test indicated that under the condition of pH=6.79 and IPXPO initial concentration 5×10−5 mol/L, the flotation recovery of chalcopyrite reached about 90%, while for pyrite only 25%, suggesting that IPXPO is an excellent collector for flotation separation and enrichment of chalcopyrite.
To obtain new phosphorescent Cu(I) complexes, the new N,S-donor organic ligand 1-methyl-4,6-diphenylpyrimidine-2(1H)-thione (mdppmt) was synthesized. Reactions of mdppmt with CuI in CH3CN and CH2Cl2 under different conditions afforded a one-dimensional polymer [{Cu(MeCN)}Cu3(μ-I)(μ3-I)3(μ3-mdppmt)]n (1) and a binuclear Cu(I) complex [{(mdppmt)Cu}(μ-I)(μ-mdppmt)(CuI)] (2). Solvothermal reactions of CuCN or CuSCN with mdppmt in MeCN and H2O at 120 °C resulted in the formation of a two-dimensional polymer [{Cu(μ-CN)}2(μ-mdppmt)]n (3) and one one-dimensional polymeric complex [{Cu(mdppmt)}(μ-SCN)]n (4), respectively. All compounds were characterized by elemental analysis, infrared spectroscopy, thermal analysis, powder X-ray diffraction analysis and single crystal X-ray diffraction. The photoluminescent properties of 1~4 along with free mdppmt in the solid state were also studied at ambient temperature.
Under the hydro(solvo)thermal conditions, four organic bidentate bridging N,N-donor ligands 1,3-bis(2-methylimidazol-1-yl)propane (L1), 4,4'-di(1H-imidazol-1-yl)-1,1'-biphenyl (L2), 1,2-bis(2-methyl-1H-imidazol-1-ylmethyl)benzene (L3) and 5,6,7,8-tetrahydroquinoxaline (L4) were employed to react with CuBr/CuI, generating four 2-D layered copper(I)-halo coordination polymer materials [Cu4Br4(L1)2] 1, [CuI(L2)] 2, [CuI(L3)] 3 and [Cu2I2(L4)] 4. In 1-4, the different Cu-I motifs are found: cubic Cu4Br4 core in 1; castellated Cu-I single chain in 2; rhombic Cu2I2 core in 3; staircase-like Cu-I double chain in 4. The 2-D layer networks of 1-3 can all be simplified into a simple 44 topology (planar for 1 and 3; wave-like for 2), while the 2-D layer network of 4 has a 63 topology. The photoluminescence behaviors of 1-4 under the UV lamp suggest that 1 and 2 possess the fluorescence thermochromism properties. Under the UV lamp, with the decrease of the temperature, (i) 1 exhibit a yellow-to-red emission; (ii) 2 exhibits a yellow-to-green emission; (iii) 3 always emits the green light; (iv) 4 never emits light. These are further confirmed by their emission spectra. From 297 K to 77 K, the emission of 1 exhibits a large red shift from 561 nm to 623 nm; the emission of 2 exhibits a large blue shift from 571 nm to 515 nm; only a minor red shift is observed for the emission of 3; no peaks appear in the emission spectra of 4. The crystal data of 1 and 2 at the different temperature have been collected for revealing the origination of their fluorescence thermochromism properties. Based on the investigations above, the effect of the rigidity/flexibility of organic ligand on the fluorescence thermochromism property of copper(I)-halo coordination polymer materials are discussed. The quantum yields at 297 K and the photoluminescence lifetimes at 297 K and 77 K for 1-3 were also measured for better understanding their photoluminescence properties.
Five new complexes containing Ag(I) salts and the ligand 3,4‐dipyridyl ketone (L34) were synthesized and characterized, namely {[AgL34]ClO4}∞ (1), {[AgL34]BF4}∞ (2), {AgL34NO3}∞ (3), {AgL34CF3CO2}∞ (4) and [AgL34CF3SO3]4 (5). Both the anion and the ligand conformation were found to affect the structure packing. This set of 1:1 M:L structures demonstrated the role of anion binding and ligand conformation in determining the molecular architecture; the increasing alignment of cations in neighboring M‐L chains in structures 1‐4 can be attributed to the anions’ ability to coordinate to Ag(I) cations. The conformation of the ligand was shown to determine whether a discrete or polymeric architecture formed. In complexes 1‐4 the N3py atom was in a cis orientation, with 1 and 2 forming offset chains held together in 2‐D sheets. The anion in 3 helped link 1‐D chains together to form double chains with the double chains offset in the 2‐D sheet. Complex 4 was present as a 2‐D sheet, with the bifurcating CF3CO2‐ anion causing the alignment of the Ag(I) cations within the sheet. Complex 5 was the only discrete species, with L34 adopting a trans arrangement and acting as corner pieces of a molecular square. DFT calculations showed that the two conformations of the free ligand had a difference in energy of only 2.1 kJ mol‐1.
In this paper, a novel surfactant, N-butoxypropyl-S-[2-(hydroxyimino) propyl] dithiocarbamate ester (BOPHPDT) was first synthesized and introduced as a flotation collector for copper minerals. The micro and bench-scale flotation results demonstrated BOPHPDT exhibited superior flotation performance for chalcopyrite in comparison with xanthates and excellent selectivity against pyrite, and the preferable pH values for its attachment to chalcopyrite surfaces were 4–8. Adsorption thermodynamics and kinetics elucidated that BOPHPDT adsorption on to chalcopyrite was a spontaneously endothermic chemisorption process. The results of in situ scanning electrochemical microscopy (SECM) and zeta potential showed that BOPHPDT might anchor on the positively charge sites of chalcopyrite surfaces to form new species. Fourier transform infrared (FTIR) spectra further elucidated that BOPHPDT might react with the Cu atoms of chalcopyrite surfaces through its CNOH and NHC(S) groups. The double chelating groups and multiple hydrophobic chains of BOPHPDT, rendered it to possess excellent affinity and hydrophobicity for improving copper minerals flotation.
The hydro(solvo)thermal reactions of CuI with diverse bisimidazole molecules were investigated, affording five new copper(I) iodides [Cu4I4(L1)2] (L1 = 1,3-bis(2-methylimidazol-1-ylmethyl)benzene) 1, [CuI(L2)] (L2 = 4,4′-bis(imidazolyl)biphenyl) 2, [Cu4I4(L3)] (L3 = 1,3-bis(2-methylimidazol-1-yl)propane) 3, [Cu4I4(L4)2] (L4 = 1,4-bis(2-ethylimidazol-1-yl)butane) 4, and [Cu4I4(L5)] (L5 = 1,4-bis(1-imidazoly)benzene) 5. X-ray single-crystal diffraction analysis reveals that (i) in 1, a tetranuclear Cu-I cluster (stepped cubane) is observed, and the L1 molecule only acts as an ancillary ligand; (ii) in 2, the L2 molecules extend the castellated Cu-I chains into a 2-D layer network with a certain thickness; (iii) in 2-D single-layer network of 3, a 1-D Cu-I column is found, which can be viewed as a longitudinal packing of stepped Cu4I4 cubanes; (vi) in 4, the L4 molecules propagate the cubic Cu4I4 cubanes into a 3-D 4-fold interpenetrated network with a cds topology; and (v) in 5, the L5 molecules link the 1-D Cu-I ribbons into a 2-D single-layer network. The photoluminescence analysis indicates that 1, 2 and 4 emit light (red light for 1; yellow light for 2 and 4), while 3 and 5 are not emissive. Their photoluminescence behaviors are confirmed to be related to the Cu···Cu interactions in the molecules.
With the help of ascorbic acid as reductant, an exceedingly rare example of visible single-crystal-to-single-crystal from CuII-framework to CuI-chain in a mild condition has been observed, which involves the metal valence tautomerism and restructuring of bonds. The two compounds exhibit the properties of solvatochromism and luminescence aggregation-induced-emission towards CH3OH, respectively.
A series of ((pyridinyl)-1H-pyrazolyl)pyridine (pypzpy) ligands in which the pyrazolyl ring at 1- and 3-positions is modified by two 2-, 3-, or 4-pyridyl groups were prepared. Reaction of CuI with 2-(1-(pyridin-2-yl)-1H-pyrazolyl)pyridine (2,2'-pypzpy) in MeCN at room temperature or solvothermal reaction of the same components at 120 ºC afforded one binuclear complex [{(2,2'-pypzpy)Cu}(μ-I)]2 (1). Treatment of CuI with 3-(1-(pyridin-2-yl)-1H-pyrazolyl)pyridine (3,2'-pypzpy) at room temperature or at 120 ºC produced one dimensional (1D) polymer [{Cu3(μ3-I)3}(μ-3,2'-pypzpy)]n (2) and one two-diemensional (2D) polymer [{Cu2(μ-I)(μ3-I)}2(3,2’-pypzpy)2]n (3), respectively. Similar reactions of CuI with 4-(1-(pyridin-2-yl)-1H-pyrazolyl)pyridine (4,2'-pypzpy) at room temperature or at 150 ºC yielded one 1D polymeric complex [{Cu(μ3-I)}2(4,2'-pypzpy)2{Cu(μ-I)}2]n (4). Complexes [{Cu3(μ3-I)3}(μ-2,3'-pypzpy)]n (5), [(CuI)(μ-2,3'-pypzpy)]2 (6), [(Cu2I2)(3,3'-pypzpy)] (7), [(CuI)(4,3'-pypzpy)] (8), [{Cu(μ3-I)}2(μ-2,4'-pypzpy)2{Cu(μ-I)}2]n (9), [(CuI)(3,4'-pypzpy)] (10) and [(CuI)(μ-4,4'-pypzpy)]n (11) could be isolated by solution reactions or solvothermal reactions of CuI with 2-, 3-, 4-(1-(pyridin-3-yl)-1H-pyrazolyl)pyridine (2,3'-, 3,3'-, 4,3'-pypzpy), or 2-, 3, 4-(1-(pyridin-4-yl)-1H-pyrazolyl)pyridine (2,4'-, 3,4'-, 4,4'-pypzpy). Compounds 1-11 were characterized by IR, elemental analysis, powder X-ray diffraction and single-crystal X-ray crystallography. Complex 1 contains a normal [Cu(μ-I)]2 dimeric structure. Complexes 2 and 5 consist of an unique displaced staircase chain [Cu2(μ3-I)2]n. Complex 3 has a 2D network formed by linking chair-like [Cu2(μ-I)(μ3-I)]2 units with two pairs of 3,2'-pypzpy bridges. Complexes 4 and 9 have a rare 1D triple chain, in which one internal 1D ladder-like chain [Cu2(μ3-I)2]n is connected with two zigzag chains [Cu(μ-I)]n via 4,2'-pypzpy or 2,4'-pypzpy ligands. Compound 6 consists of two [CuI] units interconnected by two 2,3'-pypzpy ligands. Compound 11 contains a 1D chain assembled by monomeric [CuI] units and 4,4'-pypzpy ligands. The luminescence properties of 1−11 in solid state were also investigated at room temperature. These results offer an interesting insight into how the coordination sites of the pypzpy ligands do exert great impact on their coordination modes, the coordination spheres of the Cu(I) centers, the formation of the [CunIn] motifs and the topological structures of the final complexes.
