Frame/skeleton-like nanostructures are of great value in plasmonic catalysis as a result of the synergetic structural advantages arising from both maximized surface atomic exposure and efficient incident light absorptions. Herein, we report the size-tunable fabrication of yolk-shell AuAg nanoparticles containing a spherical core and cuboctahedral skeletons (AuAg YSCNSs), together with the exploration of their applications for assisting the reduction of 4-nitrophenol (4-NP) under ultraviolet-visible (UV-vis) light irradiation. The use of glutathione (GSH) at an appropriate amount to mediate the galvanic replacement reaction between Au@Ag core-shell nanocubes and HAuCl4 is found to be crucial in regulating the shape evolution. Their sizes could be readily tuned by altering the edge lengths of Au@Ag core-shell nanocubes. When working as the photocatalyst assisting the reduction of 4-NP, the AuAg YSCNSs exhibit a higher apparent rate constant under UV-vis light irradiation. The current work demonstrates the feasibility to create skeleton-like noble metal nanocrystals with the shape largely deviated from that of the original template via the "top-down" carving strategy by introducing non-metallic surface doping, which could be potentially extended to other noble metals or alloys.
Ultrasmall gold nanoparticles (NPs) stabilized in networks by polymantane ligands (diamondoids) were successfully used as precatalysts for highly selective heterogeneous gold-catalyzed dimethyl allyl(propargyl)malonate cyclization to 5-membered conjugated diene. Such reaction usually suffers from selectivity issues with homogeneous catalysts. This control over selectivity further opened the way to one-pot cascade reaction, as illustrated by the 1,6-enyne cycloisomerization-Diels-Alder reaction of dimethyl allyl propargyl malonate with maleic anhydride. The ability to assemble nanoparticles with controllable sizes and shapes within networks concerns research in sensors, medical diagnostics, information storage, and catalysis applications. Herein, the control of the synthesis of sub-2-nm gold NPs is achieved by the formation of dense networks, which are assembled in a single step reaction by employing ditopic polymantanethiols. By using 1,1'-bisadamantane-3,3'-dithiol (BAd-SH) and diamantane-4,9-dithiol (DAd-SH), serving both as bulky surface stabilizers and short-sized linkers, we provide a simple method to form uniformly small gold NPs (1.3 ± 0.2 nm to 1.6 ± 0.3 nm) embedded in rigid frameworks. These NP arrays are organized alongside short interparticular distances ranging from 1.9 to 2.7 nm. The analysis of gold NP surfaces and their modification were achieved in joint experimental and theoretical studies, using notably XPS, NMR, and DFT modeling. Our experimental studies and DFT analyses highlighted the necessary oxidative surface reorganization of individual nanoparticles for an effective enyne cycloisomerization. The modifications at bulky stabilizing ligands allow surface steric decongestion for the alkyne moiety activation but also result in network alteration by overoxidation of sulfurs. Thus, sub-2-nm nanoparticles originating from networks building create convenient conditions for generating reactive Au(I) surface single-sites-in the absence of silver additives-useful for heterogeneous gold-catalyzed enyne cyclization. These nanocatalysts, which as such ease organic products separation, also provide a convenient access for building further polycyclic complexity, owing to their high reactivity and selectivity.
A convenient and efficient approach for the formation of nitrogen heterocycle-fused imidazo[1,2-a]pyridine and benzo[b]selenophenes has been developed through copper-catalyzed direct selenylation of readily available 2-(2-bromophenyl)imidazo[1,2-a]pyridines via regioselective cleavage of C(sp2)-Br and C(sp2)-H bonds using readily available selenium powder as the selenylating reagents under ligand- and base-free conditions in air. Preliminary mechanistic investigations indicated that radical species were involved in the present transformation.
