title: Atom transfer radical polymerization preparation and photophysical properties of polypyridylruthenium derivatized polystyrenes.
abstract: A ruthenium containing polymer featuring a short carbonyl-amino-methylene linker has been prepared by atom transfer radical polymerization (ATRP). The polymer was derived from ATRP of the N-hydroxysuccinimide (NHS) derivative of p-vinylbenzoic acid, followed by an amide coupling reaction of the NHS-polystyrene with Ru(II) complexes derivatized with aminomethyl groups (i.e., [Ru(bpy)2(CH3-bpy-CH2NH2)](2+) where bpy is 2,2'-bipyridine, and CH3-bpy-CH2NH2 is 4-methyl-4'-aminomethyl-2,2'-bipyridine). The Ru-functionalized polymer structure was confirmed by using nuclear magnetic resonance and infrared spectroscopy, and the results suggest that a high loading ratio of polypyridylruthenium chromophores on the polystyrene backbone was achieved. The photophysical properties of the polymer were characterized in solution and in rigid ethylene glycol glasses. In solution, emission quantum yield and lifetime studies reveal that the polymer's metal-to-ligand charge transfer (MLCT) excited states are quenched relative to a model Ru complex chromophore. In rigid media, the MLCT-ground state band gap and lifetime are both increased relative to solution with time-resolved emission measurements revealing fast energy transfer hopping within the polymer. Molecular dynamics studies of the polymer synthesized here as well as similar model systems with various spatial arrangements of the pendant Ru complex chromophores suggest that the carbonyl-amino-methylene linker probed in our target polymer provides shorter Ru-Ru nearest-neighbor distances leading to an increased Ru*-Ru energy hopping rate, compared to those with longer linkers in counterpart polymers.
authors.affiliation: Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599, United States.
authors.forename: Zhen
authors.initials: Z
authors.lastname: Fang
authors.forename: Akitaka
authors.initials: A
authors.lastname: Ito
authors.forename: Shahar
authors.initials: S
authors.lastname: Keinan
authors.forename: Zuofeng
authors.initials: Z
authors.lastname: Chen
authors.forename: Zoe
authors.initials: Z
authors.lastname: Watson
authors.forename: Jason
authors.initials: J
authors.lastname: Rochette
authors.forename: Yosuke
authors.initials: Y
authors.lastname: Kanai
authors.forename: Darlene
authors.initials: D
authors.lastname: Taylor
authors.forename: Kirk S
authors.initials: KS
authors.lastname: Schanze
authors.forename: Thomas J
authors.initials: TJ
authors.lastname: Meyer
mesh_terms: D004563:Electrochemistry; D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D009942:Organometallic Compounds / Q000737:chemistry*; D058105:Polymerization; D011137:Polystyrenes / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D011137:Polystyrenes; D011725:Pyridines; D012428:Ruthenium; C023666:pyridine