136157-01-2

Upstream product

• 64443-05-6 tetrakis(actonitrile)copper(I) hexafluorophosphate 
• 192463-40-4 (R)-(-)-4,12-bis(diphenylphosphino)-[2,2]-paracyclophane 
• 484-11-7 2.9-dimethyl-1,10-phenanthroline 

Downstream Products

• 467448-39-1 [Cu(2,9-dimethyl-1,10-phenanthroline)2][tetrakis(3,5-bis(trifluoromethylphenyl))borate] 

Relevant academic research and scientific papers

Steric vs electronic effects and solvent coordination in the electrochemistry of phenanthroline-based copper complexes

The present exhaustive electrochemical study proposes a rationalization of the redox properties of 1,10-phenanthroline-based copper complexes as a function of i) ligand molecular structure, evidencing the competition between electronic and steric effects of alkyl/aryl substituents, and ii) nature of working medium in terms of both solvent and supporting electrolyte anion. Occupancy of the 2 and 9 positions of the phenanthroline is a powerful tool to modulate the oxidation potentials of this family of complexes in a wide potential range. Solvent molecules play a key role in the metal-centred oxidative electron transfer process (unlike the optical electron transition), acting as ancillary ligands that allow the transition between tetrahedral four-coordinated Cu(I) state to tetragonal five-coordinated Cu(II). Actually clear evidences of the entry of one solvent molecule in the inner coordination sphere of the complexes are proved by the Kolthoff and Lingane method. Proof of ionic couple formation is also found.

Multidentate Phenanthroline Ligands Containing Additional Donor Moieties and Their Resulting Cu(I) and Ru(II) Photosensitizers: A Comparative Study

To bind or not to bind: Driven by the motivation to increase the (photo)stability of traditional Cu(I) photosensitizers, multidentate diimine ligands, which contain two additional donor sites, were designed. To this end, a systematic series of four 1,10-phenanthroline ligands with either OR or SR (R = iPr or Ph) donor groups at the 2 and 9 positions and their resulting hetero- A nd homoleptic Cu(I) complexes were prepared. In addition, the related Ru(II) complexes were also synthesized to study the effect of another metal center. In the following, a combination of NMR spectroscopy and X-ray analysis was used to evaluate the impact of the additional donor moieties on the coordination behavior. Most remarkably, for the homoleptic bis(diimine)copper(I) complexes, a pentacoordinated copper center, corresponding to a (4 + 1)-fold coordination mode, was found in the solid state. This additional binding is the first indication that the extra donor might also occupy a free coordination site in the excited-state complex, modifying the nature of the excited states and their respective deactivation processes. Therefore, the electrochemical and photophysical properties of all novel complexes (in total 13) were studied in detail to assess the potential of these photosensitizers for future applications within solar energy conversion schemes. Finally, the photostabilities and a potential degradation mechanism were analyzed for representative samples.

Heteroleptic Copper Photosensitizers: Why an Extended π-System Does Not Automatically Lead to Enhanced Hydrogen Production

A series of heteroleptic copper(I) photosensitizers of the type [(P^P)Cu(N^N)]+with an extended π-system in the backbone of the diimine ligand has been prepared. The structures of all complexes are completely characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography. These novel photosensitizers were assessed with respect to the photocatalytic reduction of protons in the presence of triethylamine and [Fe3(CO)12]. Although the solid-state structures and computational results show no significant impact of the π-extension on the structural properties, decreased activities were observed. To explain this drop, a combination of electrochemical and photophysical measurements including time-resolved emission as well as transient absorption spectroscopy in the femto- to nanosecond time regime was used. Consequently, shortened excited state lifetimes caused by the rapid depopulation of the excited states located at the diimine ligand are identified as a major reason for the low photocatalytic performance.

Highly efficient thermally activated fluorescence of a new rigid Cu(i) complex [Cu(dmp)(phanephos)]+

The rigid [Cu(dmp)(phanephos)]+ complex displays a high luminescence quantum yield of 80% at ambient temperature. In contrast to the long-lived phosphorescence of 240 μs at T a radiative rate of kr = 3 × 103 s-1, the ambient-temperature emission represents a thermally activated delayed fluorescence (DF) with a decay time of only 14 μs and a radiative rate of kr(DF) = 6 × 104 s-1. Evidence for the involvement of the excited singlet state in the emission process is presented. This material has high potential to be applied in efficient OLEDs taking advantage of the singlet harvesting mechanism. The Royal Society of Chemistry 2013.

Sulfonylation of Aryl Halides by Visible Light/Copper Catalysis

An efficient visible-light-assisted, copper-catalyzed sulfonylation of aryl halides with sulfinates is reported. In our protocol, a single ligand CuI photocatalyst formed in situ was used in the photocatalytic transformation. Diverse organosulfones were obtained in moderate to good yields. This strategy demonstrates a promising approach toward the synthesis of diverse and useful organosulfones.

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.

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