Robust proton-independent electron reservoirs of (ferrocenylmethyl) trimethylammonium chloride and Na 4 [Fe(CN) 6 ] are utilized to separate H 2 evolution from O 2 evolution with much lower voltage inputs than that of conventional water-splitting electrolysis. Such decoupled water splitting can be readily driven by photovoltaics with small photovoltages in near-neutral solution under natural sunlight irradiation. The electron reservoirs can facilitate sustainable H 2 production from decoupled water splitting and further integrate H 2 evolution with organic upgrading, yielding two value-added products (H 2 and 2,5furandicarboxylic acid).

We present a strong correlation of the Ni(salophen) structure and properties measured in single-molecule vs bulk quantities and in ultra high vacuum vs solution phase. Under a scanning tunneling microscope (STM), Ni(salophen) forms a self-assembled monolayer (SAM) on Au(111) at 23 °C with molecular structure identical to that of the X-ray crystallographic measurement. The HOMO and LUMO levels are determined using elastic tunneling spectroscopy at the single-molecule level with confirmation by monolayer-quantity ultraviolet photoelectron spectroscopy (UPS) and by cyclic voltammetry (CV) measurements. The STM-determined HOMO− LUMO gap of 3.28 eV and (HOMO−1)−HOMO gap of 0.36 eV form a new foundation for the selection of hybrid functionals with a simple basis set to be effective in accurately calculating single-molecule Ni(salophen) frontier MO levels. Our results suggest that microscopy-based experiments on a surface, along with free-molecule gas-phase calculations, can provide useful insights into the physical properties of metal(salen) complexes, especially when such direct measurements are not available in solution.Letter pubs.acs.org/JPCL

The synthesis and characterization of three new organic hydrazines containing BODIPY dyes and the respective aminomethyl complexes is described.