Tris 2 2 bipyridyl dichlororuthenium 2 hexahydrate

Reactions were performed in oven-dried round-bottomed flasks unless otherwise noted. Reactions that required an inert atmosphere were conducted under a positive pressure of N₂ using flasks fitted with Suba-Seal rubber septa. Air and moisture sensitive reagents were transferred using standard syringe or cannula techniques. Column chromatography was performed with 40–63 μm silica gel with the eluent reported. Analytical thin-layer chromatography (TLC) was performed on precoated glass plates and visualized by UV or by staining with KMnO₄. Tris(2,2-bipyridyl)-dichlororuthenium(II) hexahydrate, (Ferrocenylmethyl)-trimethylammonium iodide, and potassium phosphate monobasic were purchased from Sigma-Aldrich and used without further purification. Other reagents and solvents were purchased from Sigma-Aldrich, Acros, Fisher, Strem, or Cambridge Isotopes Laboratories. Solvents for synthesis were of reagent grade or better and were dried by passage through activated alumina and then stored over 4 Å molecular sieves prior to use.³⁹ Phenyl cyanate was prepared using published methods.⁴⁰ Nanopure water (EASYpure UF compact bioresearch water system, 18 MOhm resistance) was used to prepare all solutions for UV–visible spectroscopy, electrochemical measurements, and transient absorption spectroscopy.

Clear resin was obtained from Formlabs (Somerville, MA). Pencil graphite (0.5 mm dia., Super Hi-Polymer HB) was supplied by Pentel (Torrance, CA). Au (0.1 mm and 0.5 mm dia.) and Ag (0.5 mm dia.) wires as well as potassium ferricyanide, tris(2,2′-bipyridyl)dichlororuthenium(II) hexahydrate, tri-n-propylamine, salmon testes (ST) ds-DNA (2000 base pairs avg, 41.2% G/C), poly(diallyldimethylammonium chloride (PDDA), sodium phosphate dibasic, and sulfuric acid (98.0%) were obtained from Sigma-Aldrich (St. Louis, MO). NaCl and KCl, were purchased from J.T. Baker (Center Valley, PA). Potassium phosphate monobasic was obtained from Fisher Scientific (Pittsburgh, PA). All solutions were prepared using 18 MΩ·cm water purified by passing house-distilled water through a Hydro Service and Supplies purification system (Durham, NC).