Metal complexes exhibit distinctive optic, magnetic, and redox properties that often depend on the specific combination of metal ion and ligand(s), and both components are attractive building blocks for the construction of nanostructures on surfaces in a bottom-up approach. Surfaces usually represent a two-phase boundary (solid-liquid or liquid-air) that provides an attractive platform on which plays with metal complexes in order to design and modulate chemical functionality with potential applications in nanoscience and nanotechnology. Herein, this review focuses on the development of (i) molecular design of Ru complexes with proton-coupled electron transfer both in solution and on an ITO electrode surface, and (ii) surface modification based on redox-active Ru complexes with layer-by-layer (LbL) assembly toward molecular devices.

Proton-responsive pincer-type ligands have been used as scaffolds to realize metal–ligand cooperative transformations. Unlike most of the ligands therein, 2,6-bis(pyrazol-3-yl)pyridines (3-bpp) ensure that two protic groups point to the remaining coordination site in the pincer plane. This article reviews the coordination chemistry of 3-bpp and related tridentate ligands with emphasis on the characteristics originating from the Brønsted acidity of the peripheral NH groups. Synthesis of 3-bpp complexes, which often associated with spontaneous deprotonation of the 3-bpp ligand and aggregation of the complex to give supramolecular structures, is first described. Deprotonation of the 3-bpp complexes along with the following reactivities is then discussed. Application of the 3-bpp complexes to catalytic reactions as well as materials exhibiting spin-crossover and fluorescence is also described. Finally, pincer-type complexes bearing protic N-heterocyclic carbene side arms are briefly mentioned as relevant molecules.

Extensive investigation of functional organosilicon compounds has identified various valuable applications in materials chemistry. This review summarizes the major developments of metal-mediated coupling reactions between hydrosilanes and organic halides during the last decade with an emphasis on our recent tudies. This transformation shows good functional group compatibility, and can serve as a powerful tool for the synthesis of photofunctional organosilicon compounds. The important aspects of the experimental observations on fluorescence, OLED (organic light emitting diode), SHG (second harmonic generation), and CPL(circularly polarized luminescence) have been described.