Photochemically Controlled Electrochemical Deposition and
Dissolution of Ag0 Nanoclusters on Au Electrode Surfaces†

A photoisomerizable thiolated nitrospiropyran SP, (1a), monolayer is assembled on a Au electrode by the primary deposition of thiolated nitromerocyanine isomer 1b as a monolayer on the electrode, followed by the irradiation of the surface with visible light, λ > 475 nm. The surface coverage of nitrospiropyran units (1a) on the electrode is 2 × 10-10 molecm-2. Irradiation of the electrode with UV light, 320 nm < λ < 360 nm, results in the nitromerocyanine, MR, monolayer on the electrode that binds Ag+ ions to the phenolate units. The Ag+ ions associated with the MR monolayer undergo cyclic reduction to surface-confined Ag0 nanoclusters, and reoxidation and dissolution of the Ag0 nanoclusters to Ag+ ions associated with the monolayer are demonstrated. The electron-transfer rate constants for the reduction of Ag+ to Ag0 and for the dissolution of Ag0 were determined by chronoamperometry and correspond to ketred = 12.7 s-1 and ketox = 10.5 s-1, respectively. The nanoclustering rate was characterized by surface plasmon resonance measurements, and it proceeds on a time scale of 10 min. The size of the Ag0 nanoclusters is in the range of 2 to 20 nm. The electrochemically induced reduction of the MR−Ag+ monolayer to the MR−Ag0 surface and the reoxidation of the MR−Ag0 surface control the hydrophilic−hydrophobic properties of the surface. The advancing contact angle of the MR−Ag0-functionalized surface is 59°, and the contact angle of the MR−Ag+-monolayer-functionalized surface is 74°. Photoisomerization of the Ag0−MR surface to the Ag0−SP state, followed by the oxidation of the Ag0 nanoclusters, results in the dissolution of the Ag+ ions into the electrolyte solution.