Redox Properties of Copper(I) Complex Bearing 4,7-Diphenyl-2,9-dimethyl-1,10-phenanthroline and 1,4-Bis(diphenylphosphino)butane Ligands and Effects of Light in the Presence of Chloroform

Abstract

We have examined emission and redox properties of a copper(I) complex bearing a phenanthroline type ligand and the 1,4-bis(diphenylphosphino)butane ligand. Changes in the absorption spectra upon electrolysis and light irradiation in the presence of chloroform indicate the formation of bis(diimine)copper(I) complexes.

Copper(I) Phosphinooxazoline Complexes: Impact of the Ligand Substitution and Steric Demand on the Electrochemical and Photophysical Properties

“…The much lower yield of C3 significantly differs from all other complexes and might be caused by steric constraints (two adjacent phenyl groups) and hence kinetic instability in solution. Such instability, for example, substitution reactions in solution, is well known from sterically congested homo‐ and heteroleptic Cu I complexes …”

“…With respect to possible applications in solar energy conversion schemes a high photostability in solution is essential. Unfortunately, heteroleptic diimine‐diphosphine Cu I complexes frequently suffer from a limited stability in solution under irradiation or catalytic conditions . Irradiation of the prototype photosensitizer [(P^P)Cu(N^N)]PF 6 (P^P=xantphos and N^N=bathocuproine) in acetonitrile with a solar light source (i.e., a 150 W Xe arc lamp) leads to ligand dissociation and the formation of the respective homoleptic complexes (Figure S14).…”

“…Unfortunately, a limited stability under operating conditions still hampers their large‐scale application in molecular solar energy conversion schemes . It is known, that in particular heteroleptic Cu I complexes of the type [(P^P)Cu(N^N)] + (with P^P representing a diphosphine and N^N a diimine ligand) can undergo ligand exchange reactions in solution upon light irradiation . This is mainly caused by the formation of thermodynamically more favored homoleptic bisdiimine complex [Cu(N^N) 2 ] + .…”

“…It is known, that in particular heteroleptic Cu I complexes of the type [(P^P)Cu(N^N)] + (with P^P representing a diphosphine and N^N a diimine ligand) can undergo ligand exchange reactions in solution upon light irradiation . This is mainly caused by the formation of thermodynamically more favored homoleptic bisdiimine complex [Cu(N^N) 2 ] + . Hence, this drawback drove the search and development of novel Cu I complexes with an increased stability, but also having other desired properties like a broad absorption in the visible and a reversible redoxchemistry …”

Impact of the Type of Reactor and the Catalytic Conditions on the Photocatalytic Production of Hydrogen Using a Fully Noble‐Metal‐Free System

“…Since this initial finding a multitude of heteroleptic CuPS have been prepared and catalytically tested to evaluate the effect of different ligands and substituents . The design, different catalytic applications and photophysical investigation of heteroleptic Cu(I) photosensitizers is an ongoing area of research that has experienced a strong development in recent years . For instance, [(xant)Cu(bcp)]PF 6 (with xant=xantphos and bcp=bathocuproine, Figure ) represents one of the most suitable candidates in terms of synthetic efforts, stability and photocatalytic activity ,.…”