183294-82-8

Upstream product

• 64443-05-6 tetrakis(actonitrile)copper(I) hexafluorophosphate 
• 15854-87-2 4-iodopyridine 
• 25677-69-4 2,9-diphenyl-1,10-phenanthroline 
• 39069-02-8 2,9-dibromo-1,10-phenanthroline 
• 66-71-7 1,10-Phenanthroline 

Relevant academic research and scientific papers

Structures of the Copper(I) and Copper(II) Complexes of 2,9-Diphenyl-1,10-phenanthroline: Implications for Excited-State Structural Distortion

The syntheses, crystal structures, and electronic absorption spectra of the copper(I) and copper(II) complexes of 2,9-diphenyl-1,10-phenanthroline (dpp) are reported. The complex [Cu(dpp)2](PF6) (1) crystallizes in space group P21lc with a = 11.081(4) ?, b = 25.491(8) ?, c = 14.263(5) ?, β = 92.84(3)°, Z = 4, and V = 4024(2) ?3. For 4813 unique data with F > 4.0σ(F), R = 5.41% and Rw = 6.43%. The coordination geometry about the copper-(I) center in [Cu(dpp)2]+ is best described as distorted tetrahedral with approximate C2 symmetry. The structure of [Cu(dpp)2]+ is largely determined by interligand π-stacking interactions that occur between the phenyl groups of one ligand and the phenanthroline moiety of the other ligand. Solution-state absorption and 1H NMR spectra indicate that the [Cu(dpp)2]+ complex is fluxional in solution, rocking between two enantiomeric structures of C2 molecular symmetry through an intermediate of Cs symmetry. The complex [Cu(dpp)2](C1C4)2 (2) crystallizes in space group P1? with a = 7.809(3) ?, b = 13.027(6) ?, c = 20.344(10) ?, α = 87.68(4)°, β = 89.16(4)°, γ = 79.26(4)°, Z = 2, and V = 2032(1) ?3. For 4943 unique data with F > 4.0σ(F), R = 5.22% and Rw = 5.37%. The coordination geometry about the copper(II) center in [Cu(dpp)2]2+ is best described as flattened tetrahedral with approximate D2 symmetry. There are no interligand π-stacking interactions in the structure of [Cu(dpp)2]2+. The four-coordinate geometry in [Cu(dpp)2]2+ persists in solution on the basis of solution-state and solid-state absorption spectroscopy. Structural distortion in the metal-to-ligand charge-transfer excited state of [Cu(dpp)2]+ is discussed on the basis of the structures of 1 and 2.

Reversible switching from a three- To a nine-fold degenerate dynamic slider-on-deck through catenation

Two dynamic slider-on-deck assemblies, i.e. a two-component threefold degenerate (k298 = 34.9 kHz) and a catenated three-component ninefold degenerate (k298 = 27.9 kHz) system, were quantitatively interconverted. Inspection of their computed structures revealed an allosteric effect on the sliding rates due to the spatial interaction between the components. This journal is

Strong Visible-Light-Absorbing Cuprous Sensitizers for Dramatically Boosting Photocatalysis

Developing strong visible-light-absorbing (SVLA) earth-abundant photosensitizers (PSs) for significantly improving the utilization of solar energy is highly desirable, yet it remains a great challenge. Herein, we adopt a through-bond energy transfer (TBET) strategy by bridging boron dipyrromethene (Bodipy) and a CuI complex with an electronically conjugated bridge, resulting in the first SVLA CuI PSs (Cu-2 and Cu-3). Cu-3 has an extremely high molar extinction coefficient of 162 260 m?1 cm?1 at 518 nm, over 62 times higher than that of traditional CuI PS (Cu-1). The photooxidation activity of Cu-3 is much greater than that of Cu-1 and noble-metal PSs (Ru(bpy)32+ and Ir(ppy)3+) for both energy- and electron-transfer reactions. Femto- and nanosecond transient absorption and theoretical investigations demonstrate that a “ping-pong” energy-transfer process in Cu-3 involving a forward singlet TBET from Bodipy to the CuI complex and a backward triplet-triplet energy transfer greatly contribute to the long-lived and Bodipy-localized triplet excited state.

A long-lived cuprous bis-phenanthroline complex for the photodynamic therapy of cancer

Copper is an earth-abundant and a biologically essential metal that offers a promising alternative to noble metals in photochemistry and photobiology. In this work, a series of sterically encumbered Cu(i) bis-phenanthroline complexes were investigated for their use in photochemotherapy (PCT). It was found that Cu(dsbtmp)2+ [dsbtmp = 2,9-disec-butyl-3,4,7,8-tetramethyl-1,10-phenanthroline] (compound 3), which possessed the longest excited state lifetime, exhibited significant in vitro photocytotoxicity on A375 (human malignant melanoma) and A549 (human lung carcinoma) cell lines. Fluorescence imaging demonstrated the significant uptake and localization of compound 3 in a perinuclear fashion. A comet assay indicated the induction of DNA damage in the dark. The DNA breaks were significantly amplified upon photoactivation. The light-induced enhancement of cytotoxicity was associated with the formation of reactive oxygen species (ROS), a known intermediate in photodynamic therapy (PDT). This successful demonstration of photocytotoxicity using long-lived cuprous phenanthroline paves the way to exploit this class of photosensitizers for PDT applications.

Aryl radical formation by copper(I) photocatalyzed reduction of diaryliodonium salts: NMR Evidence for a CuII/CuI mechanism

Photocatalyzed reduction of diaryliodonium salts was achieved by using [Cu(dpp)2][PF6] as a photoactive complex and DIPEA as a reductive quench. The application of a copper catalyst allows the generation of aryl radicals under mild conditions and maintains their reactivity for C-C bond formation processes.

Effects of sterics and electronic delocalization on the photophysical, structural, and electrochemical properties of 2,9-disubstituted 1,10-phenanthroline copper(I) complexes

The syntheses, crystal structures, electronic absorption spectra, electrochemical properties, and photophysical properties of a series of copper(I) bis(phenanthroline) complexes are reported. The phenanthroline ligands that have been prepared and investigated are the following: dop (2,9-di-(2-methylphenyl)-1,10-phenanthroline), xop (2-(2-methylphenyl)-9-(2,6-dimethylphenyl)-1,10-phenanthroline), dpep(2,9-diphenylethynyl-1,10-phenanthroline), and dmesp (2,9-dimesityl-1,10-phenanthroline). The complex [Cu(dop)2](PF6)·Et2O crystallizes in space group P1with a = 11.854(3) A, b = 14.705(3) A, c = 15.866(4) A, α = 107.81(2)°, β= 106.72(2)°, γ = 97.56(2)°, V = 2447.6(10) A3, and Z = 2. For 5739 unique data with F > 4.0σ(F), R = 7.52%. The complex [Cu(xop)2](PF6)·3/2CH3OH crystallizes in space group C2/c with a = 23.096(6) A, b = 23.387(6) A, c = 17.873(7) A, β = 100.08(3)°, V = 9505(5) A3, and Z = 8. For 5631 unique data with F > 4.0σ(F), R = 6.02%. The complex [Cu(dpep)2](PF6) crystallizes in space group P1 with a = 13.327(7) A, b = 14.114(7) A, c = 15.175(5) A, α = 87.23(4)°, β= 66.48(3)°, γ = 61.84(4)°, V = 2273(2) A3, and Z = 2. For 4851 unique data with F > 4.0σ(F) R = 5.47%. The complex [Cu(dmesp)(dpep)](PF6) crystallizes in space group Pbca with a = 14.547(6) A, b = 22.868(6) A, c = 30.659(10) A, V = 10199(6) A3, and Z = 8. For 2281 unique data with F > 4.0σ(F), R = 9.43%. The electrochemical, spectral, and structural properties of [Cu(dop)2]+ and [Cu(xop)2]+ demonstrate that the copper coordination environment is more sterically encumbered and more rigid in these two complexes than the coordination environment in the comparison molecule [Cu(dpp)2]+ (dpp = 2,9-diphenyl-1,10-phenanlhroline). A larger energy gap is predicted for [Cu(dop)2]+ and [Cu(xop)2]+ based on these data, and consequently, a blue-shifted emission is observed relative to [Cu(dpp)2]+. The room-temperature excited-state lifetimes in dichloromethane and methanol of the dop and xop complexes are shown to be shorter than the dpp complex, and these results are interpreted as due to a reduction in ligand π-electron delocalization in the former two complexes. The complexes [Cu(dpep)2]+ and [Cu(dmesp)(dpep)]+ are shown to have increased ligand π-electron delocalization relative to [Cu(dpp)2]+; however, neither complex displays room-temperature steady-state emission in dichloromethane.

Photodriven Electron and Energy Transfer from Copper Phenanthroline Excited States

Electron and energy transfer from copper 1,10-phenanthroline excited states is observed at room temperature in organic solvents. The copper phenanthroline excited states are metal-to-ligand charge-transfer in nature and have lifetimes of ～70-250 ns in dic