PMID- 22955328
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20130212
LR  - 20120925
IS  - 1477-9234 (Electronic)
IS  - 1477-9226 (Linking)
VI  - 41
IP  - 40
DP  - 2012 Oct 28
TI  - Structural, electronic and acid/base properties of [Ru(bpy(OH)2)3]2+ (bpy(OH)2 = 
      4,4'-dihydroxy-2,2'-bipyridine).
PG  - 12514-23
AB  - We have synthesized the complex [Ru(bpy(OH)(2))(3)](2+) (bpy(OH)(2) = 
      4,4'-dihydroxy-2,2'-bipyridine) containing ligands that can be readily 
      deprotonated. Both experimental and computational techniques were utilized to 
      perform a thorough analysis of the structural and electronic properties of the 
      complex in both the protonated and deprotonated state. The complex 
      [Ru(bpy(OMe)(2))(3)](2+) (bpy(OMe)(2) = 4,4'-dimethoxy-2,2'-bipyridine) was also 
      synthesized and studied, because the bpy(OMe)(2) ligand has electron-donating 
      properties like bpy(OH)(2), but does not contain deprotonatable groups. Cyclic 
      voltammetry of [Ru(bpy(OH)(2))(3)](2+) yields a reversible Ru(III/II) wave that 
      shifts 1.43 V to lower energy upon deprotonation of the complex. UV/Visible 
      absorbance spectroscopy reveals several Metal-to-Ligand Charge Transfer (MLCT) 
      transitions that shift to lower energy upon deprotonation of the complex. This 
      observation is in contrast to mixed-ligand systems containing deprotonatable 
      groups, such as [Ru(bpy)(2)(bpy(OH)(2))](2+) (bpy = 2,2'-bipyridine) that 
      demonstrate different types of electronic transitions assigned as mixed 
      Metal-Ligand to Ligand Charge Transfer (MLLCT). The more symmetrical nature of 
      the tris-bpy(OH)(2) complex most likely prevents the metal molecular orbitals 
      from significantly mixing with the molecular orbitals of the deprotonated ligand. 
      Luminescence studies were carried out on [Ru(bpy(OH)(2))(3)](2+) and reveal a 
      shift to lower energy and quenching of the excited state upon deprotonation in 
      accordance with the energy gap law.
FAU - Fuentes, Michelle J
AU  - Fuentes MJ
AD  - Department of Chemistry, Villanova University, Villanova, Pennsylvania 19085, 
      USA.
FAU - Bognanno, Richard J
AU  - Bognanno RJ
FAU - Dougherty, William G
AU  - Dougherty WG
FAU - Boyko, Walter J
AU  - Boyko WJ
FAU - Kassel, W Scott
AU  - Kassel WS
FAU - Dudley, Timothy J
AU  - Dudley TJ
FAU - Paul, Jared J
AU  - Paul JJ
LA  - eng
PT  - Journal Article
PL  - England
TA  - Dalton Trans
JT  - Dalton transactions (Cambridge, England : 2003)
JID - 101176026
EDAT- 2012/09/08 06:00
MHDA- 2012/09/08 06:01
CRDT- 2012/09/08 06:00
PHST- 2012/09/08 06:00 [entrez]
PHST- 2012/09/08 06:00 [pubmed]
PHST- 2012/09/08 06:01 [medline]
AID - 10.1039/c2dt31706k [doi]
PST - ppublish
SO  - Dalton Trans. 2012 Oct 28;41(40):12514-23. doi: 10.1039/c2dt31706k.