“Host–guest” binding of a luminescent dinuclear Au(i) complex based on cyclic diphosphine with organic substrates as a reason for luminescence tuneability

Abstract

A dinuclear Au(i) complex with cyclic diphosphine is a versatile platform for different luminescence responses to nucleophilic and electrophilic molecules in solutions.

Pyridyl Containing 1,5-Diaza-3,7-diphosphacyclooctanes as Bridging Ligands for Dinuclear Copper(I) Complexes

“…This, in turn, results in increase of the energy gap between T 1 and S 0 states and the abovementioned blue shift of the emission maximum. Similar conformational effects have been found recently in related luminescent dinuclear Au I complexes , . It is of interest that neither R = CH(Me)Ph nor R = CHPh 2 induce any steric strain in molecules 3 or 4 , respectively.…”

“…In these ligands the proximity of the N‐donor atom of the pyridyl group to phosphorus donor atoms disables the P,N‐coordination and thus, these ligands coordinate the transition metals in P,P‐chelate mode as other 1,5‐diaza‐3,7‐diphosphacyclootanes . In gold(I) complexes with a P‐coordination of a ligand the close disposition of pyridyl groups to the central metal atoms is responsible for the luminescent properties , . Commonly 1,5‐diaza‐3,7‐diphosphacyclooctanes serve as P,P‐chelate ligands in the Ni, Pt, Pd, Co, and Fe transition metals complexes .…”

Binuclear Gold(I) Phosphine Alkynyl Complexes Templated on a Flexible Cyclic Phosphine Ligand: Synthesis and Some Features of Solid-State Luminescence

“…Complexes 1 – 5 were characterized in solution using 1 H and 31 P­{ 1 H} NMR spectroscopy. The signals in the 1 H NMR spectra of 1 – 5 in the aromatic range are assigned to the PNNP ligand protons, which fully repeats the corresponding part of the gold­(I) chloride complex. , 1 H NMR spectra indicate the ligand conformation with C 2 idealized symmetry in solution, which can be established as a “crown” (chair–chair) conformation. The protons of the alkynyl part are registered in the typical ranges. ,− The relative integral intensity of the alkynyl and PNNP ligand proton signals provides support for formation of the dinuclear gold­(I) complexes 1 – 5 with a ratio of PNNP :{AuCCR} = 1:2.…”

“…Compared to the [ PNNP (AuCl) 2 ] complex considered earlier, , the complexes studied in this work possess a far greater potential for structural flexibility, especially when the molecule is in an excited state. For complexes 1 and 5 , this potential was analyzed in detail via DFT calculations using full and partial geometry optimizations for a whole range of possible Au–Au separation values.…”

Trialkylammonium salt degradation: implications for methylation and cross-coupling

“…Applications and divergent reactivity of trialkylammonium salts Trialkylammonium (specically N,N,N-trimethylanilinium) salts have found wide-ranging applications in synthesis, spanning phase-transfer catalysis, 1 supramolecular ion-pairing catalysis, 2,3 host-guest binding studies, 4 O-methylation, 5 O-arylation, 6 heteroatom arylations, 7 C-H methylation, 8 C-arylation, [9][10][11] uorine radiolabeling, [12][13][14][15] organometallic ligand design, [16][17][18][19][20][21] antimicrobial polymer design, 22 arene reduction, 23 pH sensing, 24 and a range of metal-catalysed cross-coupling methodologies. [25][26][27][28][29][30][31][32] The dichotomy of arylation versus methylation reactivity, while important for optimising the above-listed applications, is rarely studied in detail.…”