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Complexation of tetraphenyltetrabenzoporphine with Cu(II), Cd(II), Zn(II), and Co(II) salts in organic solvents

The rate and activation parameters of tetraphenyltetrabenzoporphine (H 2TPTBP) complexation with 3d-metal acetates and acetylacetonates are shown to be determined by the solvent nature. With an increase in the electron-donor properties of a solvent, the reaction rate increases due to protonation of N-H bonds and decreases as MAm(Solv)n – m salt solvates become more stable. As the result, the rate of a reaction with ZnAc2 increases in the series: DMF < DMSO < Py < PrOH-1 < CH3CN < C6H6. In inert and weakly coordinating solvents, the transition state of a reaction is supposed to be formed according to the mechanism of contraction of the salt coordination sphere. The rate of H2TPTBP reaction with metal acetates in pyridine changes in the series: Cu(II) > Cd(II) > Zn(II) > Co(II), while the stability of the obtained complexes decreases in the series Cu(II) > Co(II) > Zn(II) > Cd(II). It is shown that the spectral criterion of the complex stability can be used in the series of metal complexes with one ligand, but it is violated if the ligand structure is changed.

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

 

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Aromatic Thiocyanation using Supported Copper(I) Thiocyanate

Charcoal Supported copper(I) thiocyanate can be used to convert bromo- and iodo-benzenes into phenyl thiocyanates with no contamination from phenyl isothiocyanates.

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

 

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Effect of metal oxidation state on FRET: A Cu(i) silent but selectively Cu(ii) responsive fluorescent reporter and its bioimaging applications

Copper(ii) and copper(i) complexes of a newly designed and crystallographically characterized Schiff base (HL) derived from rhodamine hydrazide and cinnamaldehyde were isolated in pure form formulated as [Cu(L)(NO3)] (L-Cu) (1) and [Cu(HL)(CH3CN)(H2O)]ClO4 (HL-Cu) (2), and characterized by physicochemical and spectroscopic tools. Interestingly, complex 1 but not 2 offers red fluorescence in solution state, and eventually HL behaves as a Cu(ii) ions selective FRET based fluorosensor in HEPES buffer (1 mM, acetonitrile-water: 1/5, v/v) at 25 C at biological pH with almost no interference of other competitive ions. The dependency of the FRET process on the +2 oxidation state of copper has been nicely supported by exhaustive experimental studies comprising electronic, fluorimetric, NMR titration, and theoretical calculations. The sensing ability of HL has been evaluated by the LOD value towards Cu(ii) ions (83.7 nM) and short responsive time (5-10 s). Even the discrimination of copper(i) and copper(ii) has also been done using only UV-Vis spectroscopic study. The efficacy of this bio-friendly probe has been determined by employing HL to detect the intercellular distribution of Cu(ii) ions in HeLa cells by developing image under fluorescence microscope. This journal is

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

 

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Desymmetrization of meso-N-sulfonylaziridines with chiral nonracemic nucleophiles and bases

The cyclohexene-derived aziridine 7-tosyl-7-azabicyclo[4.1.0]heptane (1) reacts with Grignard reagents in the presence of chiral nonracemic Cu-catalysts to afford sulfonamides 3a-e in up to 91% ee under optimized conditions. No activation of the aziridine by Lewis acids is required. The reaction may be extended to other bicyclic N-sulfonylated aziridines, but aziridines derived from acyclic olefins, cyclooctene, and trinorbornene are unreactive under standard conditions. Exposure of 1 to s-BuLi in the presence of (-)-sparteine (2.8 equiv.) affords the allylic sulfonamide 31 in 35% yield and 39% ee. Under the same conditions, the aziridines 33 and 35 yield products 34 and 36 derived from intramolecular carbenoid insertion with 75 and 43% ee, respectively.

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

 

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Surface properties of lead-free halide double perovskites: Possible visible-light photo-catalysts for water splitting

Halide double perovskites based on combinations of monovalent and trivalent cations have been proposed as promising lead-free alternatives to lead halide perovskites. Among the newly synthesized compounds Cs2BiAgCl6, Cs2BiAgBr6, Cs2SbAgCl6, and Cs2InAgCl6, some exhibit bandgaps in the visible range and all have low carrier effective masses; therefore, these materials constitute potential candidates for various opto-electronic applications. Here, we use first-principles calculations to investigate the electronic properties of the surfaces of these four compounds and determine, for the first time, their ionization potential and electron affinity. We find that the double perovskites Cs2BiAgCl6 and Cs2BiAgBr6 are potentially promising materials for photo-catalytic water splitting, while Cs2InAgCl6 and Cs2SbAgCl6 would require controlling their surface termination to obtain energy levels appropriate for water splitting. The energy of the halogen p orbitals is found to control the conduction band level; therefore, we propose that mixed halides could be used to fine-tune the electronic affinity.

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

 

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Planar perovskite solar cells employing copper(I) thiocyanate/N,N?-di(1-naphthyl)-N,N?-diphenyl-(1,1?-biphenyl)-4,4?-diamine bilayer structure as hole transport layers

Organic hole transport materials, such as N 2,N 2,N 2?,N 2?,N 7,N 7,N 7?,N 7?-octakis(4-methoxyphenyl)-9,9?-spirobi[9H-fluorene]-2,2?,7,7?-tetramine (Spiro-OMeTAD), are commonly used as the hole transport materials in efficient perovskite solar cells, but the chemical synthetic procedure may increase the cost of the photovoltaic devices. On the other hand, inorganic hole transport materials, such as copper(I) thiocyanate (CuSCN) or copper(I) iodide (CuI), have potential for the manufacture of efficient and low-cost perovskite solar cells, but the performance of these devices is still imperfect. In this study, we demonstrate the use of an inorganic CuSCN and organic N,N?-di(1-naphthyl)-N,N?-diphenyl-(1,1?-biphenyl)-4,4?-diamine (NPB) hybrid bilayer as an alternative hole transport layer for planar CH3NH3PbI3 perovskite solar cells. The electronic behavior of the bilayer and the performance of the corresponding devices were discussed. As a result, the power conversion efficiency (PCE) for the best cells at AM1.5G illumination with a shadow mask was 12.3%.

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

 

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Formation of a disorderd hetero-junction by diffusion of CuI from CuSCN into In2S3 layers: A surface photovoltage study

Charge-selective disordered hetero-junctions were formed in evaporated In2S3 layers by diffusing at 200 C CuI from a CuSCN source. The thicknesses of In2S3 layers and diffusion times were varied between 5 and 80 nm and between 2 and 19 min, respectively. In some cases CuSCN layers were etched back with pyridine. Spectral and time-dependent surface photovoltage measurements were carried out in the capacitor arrangement. It was observed that a competing process of charge separation and relaxation was initiated together with the formation of the charge-selective In2S3/In2S3:Cu hetero-junction. Modulated SPV amplitude for different annealing times and thicknesses of the evaporated In2S3 layers. Copyright

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

 

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Understanding of perovskite crystal growth and film formation in scalable deposition processes

Hybrid organic-inorganic perovskite photovoltaics (PSCs) have attracted significant attention during the past decade. Despite the stellar rise of laboratory-scale PSC devices, which have reached a certified efficiency over 25% to date, there is still a large efficiency gap when transiting from small-area devices to large-area solar modules. Efficiency losses would inevitably arise from the great challenges of homogeneous coating of large-area high quality perovskite films. To address this problem, we provide an in-depth understanding of the perovskite nucleation and crystal growth kinetics, including the LaMer and Ostwald ripening models, which advises us that fast nucleation and slow crystallization are essential factors in forming high-quality perovskite films. Based on these cognitions, a variety of thin film engineering approaches will be introduced, including the anti-solvent, gas-assisted and solvent annealing treatments, Lewis acid-base adduct incorporation, etc., which are able to regulate the nucleation and crystallization steps. Upscaling the photovoltaic devices is the following step. We summarize the currently developed scalable deposition technologies, including spray coating, slot-die coating, doctor blading, inkjet printing and vapour-assisted deposition. These are more appealing approaches for scalable fabrication of perovskite films than the spin coating method, in terms of lower material/solution waste, more homogeneous thin film coating over a large area, and better morphological control of the film. The working principles of these techniques will be provided, which direct us that the physical properties of the precursor solutions and surface characteristics/temperature of the substrate are both dominating factors influencing the film morphology. Optimization of the perovskite crystallization and film formation process will be subsequently summarized from these aspects. Additionally, we also highlight the significance of perovskite stability, as it is the last puzzle to realize the practical applications of PSCs. Recent efforts towards improving the stability of PSC devices to environmental factors are discussed in this part. In general, this review, comprising the mechanistic analysis of perovskite film formation, thin film engineering, scalable deposition technologies and device stability, provides a comprehensive overview of the current challenges and opportunities in the field of PSCs, aiming to promote the future development of cost-effective up-scale fabrication of highly efficient and ultra-stable PSCs for practical applications.

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

 

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Transition metal complexes containing the S(NtBu)42- tetraimidosulfate dianion

Three novel metal complexes [(acac)2Cu2(NtBu)4S] (3), [Li(thf)4]2[I4Cd2(NtBu)4S] (4) and [(thf)2Li{(SiMe3)2N}Zn(NtBu)4S] (5) are prepared from the intended transmetalation of the dilithium complex of N,N?,N??,N???-tetrakis(tert-butyl)tetraimidosulfate [(thf)4Li2(NtBu)4S] (1). The two lithium cations are replaced by either the cationic (acac)Cu(ii) moiety, the neutral I2Cd(ii) residue or only a single lithium cation is substituted by the cationic (Me3Si)2NZn(ii) fragment. The complexes show two main results: first the S(NtBu)42- tetrahedron can serve as a ligand to transition metals from the soft Cu(ii) to the harder Zn(ii) at opposite sides and second the S-N bond distances vary only marginally in response to the various metals and the four distances constantly sum up to 6.38(2) A. Hence the electropositive sulfur atom responds by internal shift to the metal-polarized negative charge at the outside of the S(NR)42- tetrahedron. This journal is

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

 

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Oxidation of metallic copper with complexones in organic media

Direct oxidation of copper in organic media with complexones (sterically hindered o-quinones; acetylacetone and pyridine as stabilizing ligands) was studied. From the complexes obtained, the initial components can be regenerated.

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