18511-71-2Relevant articles and documents
Sugar-Assisted Chirality Control of Tris(2,2'-bipyridine)-Metal Complexes
Nakashima, Kazuaki,Shinkai, Seiji
, p. 1267 - 1270 (1994)
2,2'-Bipyridine-4,4'-diboronic acid (2), a 2,2'-bipyridine derivative with sugar-binding sites was synthesized.The Δ vs.A chirality of the Fe2+*23 complex was selectively generated in correlation with the absolute configuration of added saccharides.
Varying the electronic structure of surface-bound ruthenium(II) polypyridyl complexes
Ashford, Dennis L.,Brennaman, M. Kyle,Brown, Robert J.,Keinan, Shahar,Concepcion, Javier J.,Papanikolas, John M.,Templeton, Joseph L.,Meyer, Thomas J.
, p. 460 - 469 (2015)
In the design of light-harvesting chromophores for use in dye-sensitized photoelectrosynthesis cells (DSPECs), surface binding to metal oxides in aqueous solutions is often inhibited by synthetic difficulties. We report here a systematic synthesis approach for preparing a family of Ru(II) polypyridyl complexes of the type [Ru(4,4′-R2-bpy)2(4,4′-(PO3H2)2-bpy)]2+ (4,4′(PO3H2)2-bpy = [2,2′-bipyridine]-4,4′-diylbis(phosphonic acid); 4,4′-R2-bpy = 4,4′-R2-2,2′-bipyridine; and R = OCH3, CH3, H, or Br). In this series, the nature of the 4,4′-R2-bpy ligand is modified through the incorporation of electron-donating (R = OCH3 or CH3) or electron-withdrawing (R = Br) functionalities to tune redox potentials and excited-state energies. Electrochemical measurements show that the ground-state potentials, E′(Ru3+/2+), vary from 1.08 to 1.45 V (vs NHE) when the complexes are immobilized on TiO2 electrodes in aqueous HClO4 (0.1 M) as a result of increased Ru dπ-π back-bonding caused by the lowering of the π orbitals on the 4,4′-R2-bpy ligand. The same ligand variations cause a negligible shift in the metal-to-ligand charge-transfer absorption energies. Emission energies decrease from max = 644 to 708 nm across the series. Excited-state redox potentials are derived from single-mode Franck-Condon analyses of room-temperature emission spectra and are discussed in the context of DSPEC applications.
Synthesis of phosphonic acid derivatized bipyridine ligands and their ruthenium complexes
Norris, Michael R.,Concepcion, Javier J.,Glasson, Christopher R. K.,Fang, Zhen,Lapides, Alexander M.,Ashford, Dennis L.,Templeton, Joseph L.,Meyer, Thomas J.
, p. 12492 - 12501 (2013/11/19)
Water-stable, surface-bound chromophores, catalysts, and assemblies are an essential element in dye-sensitized photoelectrosynthesis cells for the generation of solar fuels by water splitting and CO2 reduction to CO, other oxygenates, or hydrocarbons. Phosphonic acid derivatives provide a basis for stable chemical binding on metal oxide surfaces. We report here the efficient synthesis of 4,4′-bis(diethylphosphonomethyl)-2,2′- bipyridine and 4,4′-bis(diethylphosphonate)-2,2′-bipyridine, as well as the mono-, bis-, and tris-substituted ruthenium complexes, [Ru(bpy) 2(Pbpy)]2+, [Ru(bpy)(Pbpy)2]2+, [Ru(Pbpy)3]2+, [Ru(bpy)2(CPbpy)]2+, [Ru(bpy)(CPbpy)2]2+, and [Ru(CPbpy)3] 2+ [bpy = 2,2′-bipyridine; Pbpy = 4,4′-bis(phosphonic acid)-2,2′-bipyridine; CPbpy = 4,4′-bis(methylphosphonic acid)-2,2′-bipyridine].
