A Series of Mixed-Ligand Cu(I) Complexes Comprising Diphosphine-Disulfide Ligands: Effects of Diphosphine Ligands on Luminescent Properties

Abstract

Mixed-ligand Cu(I) complexes have attracted attention as alternatives to the noble-and/or rare-metal complexes, because of their remarkable photofunctions. To develop mixedligand Cu(I) complexes with rich photofunctions, an investigation of a suitable combination of ligands has captured more and more research interests. Herein, we report the first examples of emissive heteroleptic diphosphine-disulfide Cu(I) complexes combined with diphosphine ligands. The systematic study using a series of diphosphine ligands revealed that large π-conjugated bridging moieties between the two P atoms in the diphosphine ligands result in higher light-emission performance. When the diphosphine ligand w a s ( R ) -B I N A P ( ( R ) -B I N A P = ( R ) -( + ) -2 , 2 ′ -b i s -(diphenylphosphino)-1,1′-binaphthyl), the Cu(I) complex had an emission quantum yield (Φ em ) of 0.13 and a long emission lifetime (τ em = 118 μs).

One-Metal/Two-Ligand for Dual Activation Tandem Catalysis: Photoinduced Cu-Catalyzed Anti-hydroboration of Alkynes

“…We rationalized that the Lewis acid species present in the reaction mixture could disrupt the tight ion pairing between a alkoxide and copper through acid–base interaction, thereby generating the photoactive cationic Cu/BINAP species having a weakly coordinating boron-ate as the counterion. 22 , 36 , 37 …”

“…Interestingly, however, the use of a stronger Lewis acid such as BF 3 ·Et 2 O (30 mol %), resulted in a clean isomerization to the anti-isomer in >98% conversion (entry 7). We rationalized that the Lewis acid species present in the reaction mixture could disrupt the tight ion pairing between a alkoxide and copper through acid–base interaction, thereby generating the photoactive cationic Cu/BINAP species having a weakly coordinating boron-ate as the counterion. ,, …”

“…We rationalized that the Lewis acid species present in the reaction mixture could disrupt the tight ion pairing between a alkoxide and copper through acid−base interaction, thereby generating the photoactive cationic Cu/BINAP species having a weakly coordinating boron-ate as the counterion. 22,36,37 Mechanistic Proposal. Although a full understanding of this tandem transformation will require further investigations, the mechanism shown in Scheme 4 accounts for the observations made to date.…”

Structural characterization and luminescence properties of trigonal Cu(i) iodine/bromine complexes comprising cation–π interactions

“…37 Additionally, upon coordination, the 31 P resonances appear as wellresolved doublets together with a relatively broadened feature as referenced to the spectrum of the free ligand, diagnostic of Cu-P bond formation. [38][39][40] Crystal structure studies…”

Crystal structure of caesium tetramethyldithioimidodiphosphinate

“…The monoanionic ligands have been investigated as ligands for both main-group elements (Silvestru & Drake, 2001;Woollins, 1996) and transition metals (Rudler et al, 1997). The widespread interest in dichalcogenoimidodiphosphinates stems from their potential uses as lanthanide shift reagents (Rudler et al, 1997), industrial catalysts (Leung et al, 2000;Yamazaki et al, 2020), luminescent materials (Ma et al, 2019) as well as in metal extraction processes (du Preez et al, 1992). As part of our ongoing research on dichalcogenoimidodiphosphinate anions, we report herein the synthesis and crystallographic study of the title compound (I).…”