Luminescent gold(I) acetylide complexes. Photophysical and photoredox properties and crystal structure of [{Au(CCPh)}₂(µ-Ph₂PCH₂CH₂PPh₂)]

Abstract

The spectroscopic and photophysical properties of three gold( 1)-acetylide complexes [N (PPh,),] -[Au(CzCPh),], [Au(PPh,)(C-CPh)] and [{Au(C-CPh)},(p-dppe)] [dppe = 1,2-bis(diphenyIphosphino)ethane] are described. X-Ray crystal analysis of the latter showed a weak metal-metal interaction in the solid state with the shortest Au -Au separation being 3.1 53(2) A. The gold(1)acetylide complexes have long-lived and emissive ,(n,n*) excited states in solutions at room temperature. The photoreaction of [Au( PPh,) (C-CPh)] with methyl viologen has been investigated by Stern-Volmer quenching and flash-photolysis experiments.

Structural and Photophysical Properties of (Phosphane)gold(I)‐Decorated 4,4′‐Diethynyl‐2,2′‐bipyridine Ligands

“…8 The 1 H and 13 C NMR spectra of the compounds were in accord with the symmetrical structure shown in Chart 1. However, it was not possible to resolve signals in any of the 13 C NMR spectra for the alkyne carbon atoms.…”

“…[ 3 -7 ] Among the first photoemissive gold(I) alkynyl complexes to be described in the literature were Ph 3 PAuC≡CPh and {PhC≡CAu} 2 (µ-dppe) (dppe = Ph 2 PCH 2 CH 2 PPh 2 ). Che and coworkers [8] showed that these species possessed long-lived and emissive excited states in CH 2 Cl 2 solution at ambient temperature, and upon going from solution to the solid state, a dramatic red shift in the emission maximum of {PhC≡CAu} 2 (µ-dppe) was observed. The presence of short (≈3.00-3.20 Å) Au...Au contacts in the solid state is thought to be fundamental to emissive behaviour.…”

Photoactive building blocks for coordination complexes: Gilding 2,2′:6′,2″-terpyridine

“…276 and 289 nm. Based on studies of related species [21,[35][36][37][38] the transitions that give rise to the observed absorption spectra are most likely to be tpy/alkyne π*←π with Au orbital participation. When irradiated at 289 nm, 4'-ethynyl-2,2':6',2"-terpyridine emits at 351 nm with a high energy shoulder at 342 nm.…”

Unique distal size selectivity with a digold catalyst during alkyne homocoupling

“…5 and Supplementary Discussion) 22,23 . X-ray Diffraction together with cyclic voltammetry studies showed that while 5a presents aurophilic bonding between two gold atoms 14 , 5c has no aurophilic bonds at all 14 and 5b has an intermediate behaviour, depending on the counteranion 24,25 . The results indicate that aurophilic bonding has a positive influence on the reaction rate but none on the distal size selectivity.…”