Metal‐Ion Permeation in Congested Nanochannels: The Exposure Effect of Ag⁺ Ions on the Phosphorescent Properties of a Gold(I)–Pyrazolate Complex that is Confined in the Nanoscopic Channels of Mesoporous Silica

Abstract

An organometallic/silica nanocomposite of a 1D cylindrical assembly of a trinuclear gold(I)-pyrazolate complex ([Au(3)Pz(3)]) that was confined inside the nanoscopic channels of hexagonal mesoporous silica ([Au(3)Pz(3)]/silica(hex)), emitted red light with a luminescence center at 693 nm upon photoexcitation at 276 nm owing to a Au(I)-Au(I) metallophilic interaction. When a film of [Au(3)Pz(3)]/silica(hex) was dipped into a solution of Ag(+) in tetrahydrofuran (THF), the resulting nanocomposite material (Ag@[Au(3)Pz(3)]/silica(hex)) emitted green light with a new luminescence center at 486 nm, which was characteristic of a Au(I)-Ag(I) heterometallic interaction. Changes in the emission/excitation and XPS spectra of Ag@[Au(3)Pz(3)]/silica(hex) revealed that Ag(+) ions permeated into the congested nanochannels of [Au(3)Pz(3)]/silica(hex), which were filled with the cylindrical assembly of [Au(3)Pz(3)].

Supramolecular Phosphorescent Trinuclear Copper(I) Pyrazolate Complexes for Vapochromic Chemosensors of Ethanol

“…4a). Such luminescent profile gave a large Stokes shift (∆λ) in 279, 304, 290, 322 and 338 nm, indicating the characteristics of phosphorescent compounds [21,[23][24][25][26][27][28][29][30][31][32][33][34]. Moreover, the luminescent decay measurements in excitation and emission maxima as shown in Fig.…”

“…Energy transfer is one of phenomena in sensing capability due to the formation of a new emission site while the former emission site is coincidentally changed to a non-emissive site [30,35]. Upon exposure to ethanol for 1 min (Fig.…”

Luminescence color switching of supramolecular assemblies of discrete molecular decanuclear gold(I) sulfido complexes

“…In a certain sense, they bear an analogy or resemblance to the interesting classes of metal nanoparticles (NPs) (60)(61)(62)(63)(64)(65)(66)(67)(68)(69) and quantum dots (QDs) (70)(71)(72)(73)(74)(75)(76) in that the properties of the nanostructured materials also show a strong dependence on their sizes and shapes. Interestingly, while the optical and spectroscopic properties of metal NPs and QDs show a strong dependence on the interparticle distances, those of polynuclear gold(I) complexes are known to mainly depend on the nuclearity and the internuclear separations of gold(I) centers within the individual molecular complexes or clusters, with influence of the intermolecular interactions between discrete polynuclear molecular complexes relatively less explored (34)(35)(36)(37)(38), and those of polynuclear gold(I) clusters not reported. Moreover, while studies on polynuclear gold(I) complexes or clusters are known , less is explored of their hierarchical assembly and nanostructures as well as the influence of intercluster aggregation on the optical properties (34)(35)(36)(37)(38).…”

“…Interestingly, while the optical and spectroscopic properties of metal NPs and QDs show a strong dependence on the interparticle distances, those of polynuclear gold(I) complexes are known to mainly depend on the nuclearity and the internuclear separations of gold(I) centers within the individual molecular complexes or clusters, with influence of the intermolecular interactions between discrete polynuclear molecular complexes relatively less explored (34)(35)(36)(37)(38), and those of polynuclear gold(I) clusters not reported. Moreover, while studies on polynuclear gold(I) complexes or clusters are known , less is explored of their hierarchical assembly and nanostructures as well as the influence of intercluster aggregation on the optical properties (34)(35)(36)(37)(38). Among the gold(I) complexes, polynuclear gold(I) chalcogenido complexes represent an important and interesting class (44)(45)(46)(47)(48)(49)(50)(51).…”

“…Among the gold(I) complexes, polynuclear gold(I) chalcogenido complexes represent an important and interesting class (44)(45)(46)(47)(48)(49)(50)(51). While directed supramolecular assembly of discrete Au 12 (52), Au 16 (53), Au 18 (51), and Au 36 (54) metallomacrocycles as well as trinuclear gold (I) columnar stacks (34)(35)(36)(37)(38) have been reported, there have been no corresponding studies on the supramolecular hierarchical assembly of polynuclear gold(I) chalcogenido clusters.…”