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Copper-Coupled Electron Transfer in Colloidal Plasmonic Copper-Sulfide Nanocrystals Probed by in Situ Spectroelectrochemistry

Copper-sulfide nanocrystals can accommodate considerable densities of delocalized valence-band holes, introducing localized surface plasmon resonances (LSPRs) attractive for infrared plasmonic applications. Chemical control over nanocrystal shape, composition, and charge-carrier densities further broadens their scope of potential properties and applications. Although a great deal of control over LSPRs in these materials has been demonstrated, structural complexities have inhibited detailed descriptions of the microscopic chemical processes that transform them from nearly intrinsic to degenerately doped semiconductors. A comprehensive understanding of these transformations will facilitate use of these materials in emerging technologies. Here, we apply spectroelectrochemical potentiometry as a quantitative in situ probe of copper-sulfide nanocrystal Fermi-level energies (EF) during redox reactions that switch their LSPR bands on and off. We demonstrate spectroscopically indistinguishable LSPR bands in low-chalcocite copper-sulfide nanocrystals with and without lattice cation vacancies and show that cation vacancies are much more effective than surface anions at stabilizing excess free carriers. The appearance of the LSPR band, the shift in EF, and the change in crystal structure upon nanocrystal oxidation are all fully reversible upon addition of outer-sphere reductants. These measurements further allow quantitative comparison of the coupled and stepwise oxidation/cation-vacancy-formation reactions associated with LSPRs in copper-sulfide nanocrystals, highlighting fundamental thermodynamic considerations relevant to technologies that rely on reversible or low-driving-force plasmon generation in semiconductor nanostructures.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Structural characterisation of metal complexes containing 1-[(4-methylphenyl)sulfonamido]-2-[(2-pyridylmethylene)amino]benzene

The interaction of 2-pyridinecarboxaldehyde with N-tosyl-1,2-diaminobenzene leads to the isolation of two different products, {3-[ethoxy(2-pyridyl)methyl]-1-[(4-methylphenyl)sulfonyl]-2-(2-pyridyl)-2,3- dihydro-1H-benzo[d]imidazole}, L1, and {1-[(4-methylphenyl)sulfonyl]-2-(2-pyridyl)-2,3-dihydro-1H-benzo[d] imidazole}, L2, but not to the expected Schiff base 1-[(4-methylphenyl)sulfonamido]-2-[(2-pyridylmethylene)amino]benzene, HL3. Two kinds of complexes, containing the potentially tridentate and monoanionic [L3]- as a ligand, were obtained by different routes. ML3(p-Tos)(H2O)n complexes (p-TosH = p-toluenesulfonic acid; M = Co, Cu, Zn; n = 1-3) have been isolated by electrolysis of a solution phase composed of L1 and p-toluenesulfonic acid, using metal plates as the anode. Metal complexes of composition ML32(H2O)n (M = Mn, Co, Cu, Zn; n = 0-2) were obtained by template synthesis from M(acac)2, 2-pyridinecarboxaldehyde and N-tosyl-1,2-diaminobenzene. All these compounds have been characterised by elemental analyses, magnetic measurements, IR, mass spectrometry and, in the case of M = Zn, by 1H NMR spectroscopy. CuL3(p-Tos)(H2O), 1, ZnL3(p-Tos)(H2O), 2, CoL32, 3, CuL32, 4 and ZnL32 · 2CH3CN, 5, were also crystallographically characterised.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Magnetic properties of chalcogenide spinel CuCr2Se4 nanocrystals

The magnetic properties of chalcogenide spinel CuCr2Se4 nanocrystals have been studied as a function of crystallite size (15-30 nm). A solution-based method is used for the facile synthesis of the nanocrystals with good size control. They have close to cubic morphology with a narrow size distribution and exhibit superparamagnetic behavior at room temperature. The Curie temperature and saturation magnetization of the nanocrystals are lower as compared with the bulk and decrease with decreasing nanocrystal size. A similar trend is observed in the paramagnetic state for the Curie-Weiss temperature and effective magnetic moment. The low temperature magnetization behavior can be qualitatively explained by spin glass dynamics.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Luminescent dipyrrinato complexes of trivalent group 13 metal ions

Although free dipyrrins (dipyrromethenes) do not strongly luminesce, certain dipyrrinato complexes of BF2 and zinc(II) are known to be intensely luminescent species. Two new dipyrrinato fluorophores, based on complexes with gallium(III) and indium(III), are described. Using a previously described meso-mesityl-substituted dipyrrin, namely 5-mesityldipyrrin (mesdpm), the complexes [Ga(mesdpm)3] and [In(mesdpm)3] were prepared and structurally characterized. The complexes display the expected octahedral geometry about the metal ions. In some solvents, such as hexanes, the complexes emit green light upon excitation with UV light at room temperature, with quantum yields of 2.4% ([Ga(mesdpm)3]) and 7.4% ([In(mesdpm)3]) and lifetimes in the low nanosecond range. Observations are consistent with assignment to ligand-localized transitions, and this interpretation is further confirmed by density functional calculations described herein. The new complexes are important additions to the widely used family of dipyrrin-based fluorescent species and show that dipyrrinato complexes containing metals other than BF2 and zinc(II) may be useful fluorophores.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Phosphate-free synthesis, optical absorption and photoelectric properties of Cu2ZnGeS4 and Cu2ZnGeSe4 uniform nanocrystals

Copper-based quaternary chalcogenide semiconductor Cu2ZnGeS 4 and Cu2ZnGeSe4 nanocrystals have been synthesized successfully via a simple and convenient one-pot phosphine-free solution approach. Oleylamine was used as both the solvent and reductant for Se or S and benefited the formation of homogeneous quaternary nanocrystals. Scanning transmission electron microscopy-EDS elemental mapping confirms the uniform spatial distribution of four elements in nanocrystals. UV-Vis absorption spectra of Cu2ZnGeS4 and Cu2ZnGeSe4 nanocrystals show strong photon absorption in the entire visible range. The photoresponsive behavior indicates the potential application of Cu 2ZnGeSe4 nanocrystals in solar energy conversion systems.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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The fused heterocyclic compound represented in formula (1) has excellent effectiveness in pest control. (In the formula, A1 represents -NR4-, etc., A2 represents a nitrogen atom, etc., R1 represents an ethyl group, a cyclopropyl group, or a cyclopropylmethyl group, R2 represents -S(O)mR6 or -C(R7)(CF3)2, R4 represents a C1-C6 alkyl group optionally having one or more halogen atoms, R6 represents a C1-C6 haloalkyl group, R7 represents a fluorine atom or a chlorine atom, and m and n each represents 0, 1 or 2.)

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Simple copper(ii) hydroxide Cu(OH)2 could act as an efficient heterogeneous catalyst for selective oxidative cross-coupling of a broad range of terminal alkynes and amides using air as a sole oxidant, giving the corresponding ynamides in moderate to high yields (56-93% yields). The Royal Society of Chemistry 2012.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Superconducting YBa2Cu3O7-delta films were prepared on yttria stabilized zirconia substrates by the dipping-pyrolysis process using metal acetylacetonates (Y/Ba/Cu=1.0/3.0/4.3) as starting materials; Tc(onset) of 97 K and Tc(end) of 89 K were achieved in the resistivity measurement for the films annealed at 950 deg C in O2.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Several compounds have been isolated from the reaction between different copper bis(acetylacetonato) derivatives and the potentially bridging ligand 2,3-bis(2-pyridyl)pyrazine (bppz). A compound of formula [Cu(tfacac) 2(bppz)] (1) is obtained when the substituted trifluoromethylacetylacetonato is used. The use of different anions and the unsubstituted acetylacetonato give rise to new derivatives of general formula [{Cu(acac))2(mu-bppz)2]X2 (X– BF4-, 2; PF6-, 3; BPh 4-, 4). In these compounds the bppz ligand is acting as a bridge by chelating one copper atom and bonding monodentate a second copper atom. The presence of anions with different coordination abilities introduces variations in the copper environment and geometry. When the non-coordinating tetraphenylborate is used different compounds depending on the nature of the solvent are obtained. The dimer 4 was isolated from a methanol/chloroform mixture, while in the absence of chloroform the monomeric compound of formula [Cu(acac)(bppz)(ROH)](BPh4)-ROH (ROH=MeOH, 5) was obtained. When ethanol was used instead of methanol the analogous derivative 6 (R=EtOH) was isolated. Both species show a mononuclear structure with the copper atom five-coordinated by the chelating acac and bppz ligands and one hydroxo group occupying the apical position. A similar environment for the copper appears in [Cu(tfacac)(bppz)(MeOH)](BPh4), 7, which shows a dimeric structure through hydrogen bonds interactions. The magnetic susceptibility data of the dimeric compounds show very weak antiferromagnetic interactions between the copper atoms, an expected fact since the bridging bppz ligand is not planar but the monodentate pyridine is more or less perpendicular to the other two aromatic rings, precluding the spin exchange via the it ligand electrons.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Synthesis of Cu2ZnSnS4 nanocrystals for use in low-cost photovoltaics

(Graph Presented) Cu2ZnSnS4 (CZTS) is a promising new material for thin-film solar cells. Nanocrystal dispersions, or solar paints, present an opportunity to significantly reduce the production cost of photovoltaic devices. This communication demonstrates the colloidal synthesis of CZTS nanocrystals and their use in fabricating prototype solar cells with a power conversion efficiency of 0.23% under AM 1.5 illumination.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”