The π-acidity/basicity of cyclic trinuclear units (CTUs): from a theoretical perspective to potential applications

Abstract

Au(i)/Ag(i)/Cu(i) cyclic trinuclear units display highly adjustable π-acidity/basicity and relevant multiple superior potential applications.

Observation of crystallisation dynamics by crystal-structure-sensitive room-temperature phosphorescence from Au(I) complexes

“…Thus, it can be concluded that 10-20-nm shift of the absorption wavelength was induced by dimer formation. The calculation results for the DT6 dimer, which have previously been reported, suggested that the electronic transitions in the excitation spectrum can be assigned to a transition from the ligand-based π-orbital to intermolecular non-covalent aurophilic bonding, i.e., a ligand-to-metal-metal charge transfer (LMMCT) transition [36][37][38][39][40][41][42][43][44][45][46] . Taking into account the allowed transitions with relatively large f values (f > 10 -2 ), the LMMCT transition was also the main electronic transition in the DT4 dimer.…”

“…Some Au(I) complexes exhibit AIE activity owing to an intermolecular interaction known as the aurophilic interaction 25,26 , in which a non-covalent Au-Au bond is formed between molecules. Because of this interaction, the luminescence of Au(I) complexes can be increased by aggregation in condensed phases [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] . We hypothesised that the introduction of multiple aurophilic interactions could further enhance the AIE activity of Au complexes [36][37][38][39][40][41][42][43][44][45][46] and enable us to visualise a crystallisation process clearly.…”

“…Because of this interaction, the luminescence of Au(I) complexes can be increased by aggregation in condensed phases [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] . We hypothesised that the introduction of multiple aurophilic interactions could further enhance the AIE activity of Au complexes [36][37][38][39][40][41][42][43][44][45][46] and enable us to visualise a crystallisation process clearly. In addition, as the luminescence arises from the aggregates, the luminescence properties of Au complexes should be quite sensitive to the aggregate structure [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42]…”

“…We hypothesised that the introduction of multiple aurophilic interactions could further enhance the AIE activity of Au complexes [36][37][38][39][40][41][42][43][44][45][46] and enable us to visualise a crystallisation process clearly. In addition, as the luminescence arises from the aggregates, the luminescence properties of Au complexes should be quite sensitive to the aggregate structure [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] . Consequently, the luminescence properties can be altered by changing the aggregate structure [29][30][31][32][33][34][35] .…”

Nature of mercury inclusion in intermediate 6‐valence electron [M@Au8Hgx(PPh3)8]n+ (M = Au, Pd, Pt; x = 0‐2) protected gold superatoms: Insights from relativistic density functional theory calculations

“…The Δ E orb stabilization from the inclusion rises to ~ − 50 kcal·mol −1 per Hg 0 atom. As a result, [M@Au 8 L 8 ] n+ can be viewed as Lewis acid species, such as [Hg 3 ( o ‐C 6 F 4 ) 3 ] and [Hg 5 (C(CF 3 ) 2 ) 5 ], and coinage metal trimers . The recent high‐yield synthesis of [PdAu 8 (PPh 3 ) 8 ] 2+ , reported by Tsukuda and coworkers, favors further experimental exploration to evaluate the incorporation of different relevant ions, such as Ag, Pb, Cd, and Zn, among others …”