To realize the molecular design of new functional silver(I) clusters, a new synthetic approach has been proposed, by which the weakly coordinating ligands NO in a Ag thiolate cluster precursor can be substituted by carboxylic ligands while keeping its inner core intact. By rational design, novel atom-precise carboxylic or amino acid protected 20-core Ag(I)-thiolate clusters have been demonstrated for the first time. The fluorescence and electrochemical activity of the postmodified Ag clusters can be modulated by alrestatin or ferrocenecarboxylic acid substitution. More strikingly, when chiral amino acids were used as postmodified ligands, CD-activity was observed for the Ag clusters, unveiling an efficient way to obtain atom-precise chiral silver(I) clusters.

Surface functionalization of polyoxometalate anions with silver(I) tert-butylethynide in an organic solution medium has been achieved for the first time using an acid-induced facile approach. The generated neutral hybrid monomeric complexes [Ag(40)(C[triple bond]C(t)Bu)(22)(CF(3)COO)(12)(V(10)O(28))].4CH(3)OH (1) and [Ag(40)(C[triple bond]C(t)Bu)(20)(CF(3)COO)(12)(Mo(6)O(22))].2CH(3)OH (2) constitute members of a new silver(I)-polyoxometalate family in which the polyoxometalate anion is embedded in a polyhedral silver(I) cluster assembled by multiple argentophilic Ag...Ag interactions.

A novel discrete open high-nuclearity nest-like silver thiolate cluster complex, [Ag33 S3 (StBu)16 (CF3 COO)9 (NO3 )(CH3 CN)2 ](NO3 ) (1), has been isolated with nitrate and S(2-) anions acting as structure-directing templates. Its similar nest-like structure has been assembled into an extended layer [Ag31 S3 (StBu)16 (NO3 )9 ]n (2) by adjustment of auxiliary ligand. More interestingly, both complexes exhibit temperature-dependent luminescence of high sensitivity with a large fluorescence enhancement (12-fold for 1, 21-fold for 2), which can be easily recognized by the naked-eye (dramatic red-shift Δ=104 nm for 1, larger Δ=113 nm for 2 at 77 K compared to those at 298 K). The correlation between luminescent thermochromism and temperature-dependent variation of the coordination modes of template NO3 (-) anion, Ag⋅⋅⋅S and Ag⋅⋅⋅Ag distances are also elucidated through variable-temperature single-crystal X-ray crystal structure (VT-SCXRD) analyses.

Ni/NiO core-shell nanowires on nickel foam (NF) are successfully synthesized using an "acid-hungry" strategy. The 3D electrode with large accessible active sites and improved conductivity, possesses an optimized ionic and electronic transport path during electrochemical processes. High areal capacitance of 1.65 F cm is obtained at an ultrahigh current density of 100 mA cm , which is 19.88 times higher than pristine NF. The direct growth of nanowires makes the present supercapacitor electrode robust for long-term cycling test. By virtue of the favorable hydrogen adsorption energies on Ni and OH energy on NiO or NiOOH, the 3D electrode exhibits high performance in hydrogen evolution reaction with 146 mV at η10 mA cm-2 and Tafel value of 72 mV dec , and oxygen evolution reaction with 382 mV at η10 mA cm-2 and Tafel value of 103 mV dec in 1 m KOH. An electrolyzer using 3D electrodes as both anode and cathode can yield a current density of 10 mA cm at 1.71 V, and possesses superior long-term stability to an electrolyzer consisting of Pt/C||Ir/C. The present work develops an effective and low-cost method for the large-scale fabrication of Ni/NiO core-shell nanowires on commercial NF, providing a promising candidate for supercapacitors, fuel cells, and electrocatalysis.