Electronic Structure and Spectroscopy of [Ru(tpy)2]2+, [Ru(tpy)(bpy)(H2O)]2+, and [Ru(tpy)(bpy)(Cl)]+

Jakubı́ková, Elena; Chen, Weizhong; Dattelbaum, Dana M.; Rein, Francisca N.; Rocha, Reginaldo C.; Martin, Richard L.; Batista, Enrique R.

doi:10.1021/ic901477m

Cited by 99 publications

(121 citation statements)

References 33 publications

Supporting

Mentioning

104

Contrasting

Unclassified

Order By: Relevance

“…In this case also, we find a similar trend, where the Ru‐Npy(central) bond length is around 2.00 Å and the Ru‐Npy(terminal) bond length is ∼2.11 Å . A comparison with the optimized geometry of the [Ru(bpy)(terpy)Cl]+ system also shows a similar trend in the Ru‐Npy distances. In case of the hydroxo complex which happens to be the dominant species at a higher pH(∼12), all the bond distances but the bond trans to the Ru‐hydroxo bond is shorter: a nice illustration of the strong π donating capability of OH − .The bond trans to the metal‐ancillary ligand bond follows the order: 3<1<2<4 .…”

Section: Resultssupporting

confidence: 76%

Ruthenium Complexes of Substituted Terpyridine and Pyridyl-quinoline Based Ligands with Ancillary Ligands: Synthesis, Characterization, Electrochemical Study and DFT Calculation

et al. 2016

View full text Add to dashboard Cite

Herein we report three novel ruthenium(II) complexes of general formula [Ru(LL′L“)](PF6)n (where L= 4’‐(9‐Anthryl)‐2,2’:6’,2”‐terpyridine, L′=2‐(2‐pyridyl)‐4‐carboxyquinoline (pcqH) and L”=Cl, n=1 (for 1), L“=SCN, n=1 (for 2) and L”=H2O, n=2 (for 3)). All the complexes were characterized by routine spectroscopic techniques e. g., FTIR, UV‐Vis, mass and NMR. A detailed pH based spectroscopic and electrochemical analysis for the complexes 1,2 and 3 were carried out to determine the pka of carboxyl and aqua moiety coordinated to ruthenium centre. The COOH group in complex 2 (pkCOOH=3.13) is slightly more acidic than in complex 3 (pkCOOH=3.98). Whereas pkH2O for complex 1 (12.33) and 3 (12.27) are comparable as expected. A Pourbaix diagram for the aqua complex has been reported. The lability of the Chloro moiety in aqueous medium has been corroborated with D2O exchange 1H‐NMR study. Photovoltaic measurements for the Chloro and thiocyanato complex are also carried out. During the pH based spectrochemical and electrochemical study we find in‐situ conversion of the aqua complex into hydroxo complex. A detailed TDDFT analysis of all the three synthesized complexes and in‐situ generated hydroxo complex in the aqueous medium at higher pH has been performed to explain the various experimental findings. In the electronic spectrum all the molecules show a MLCT transition in the visible region (1: 529 nm, 2: 511 nm, 3: 488 nm). The remarkable blue shift on going from 1 to 2 to 3 is because of the decreasing stabilizing effect of the dπ (Ru) orbital (H2O > SCN > Cl). All the electronic transitions have been nicely correlated with the TDDFT analysis. Preliminary electrochemical experiment indicates that the aqua complex 3, may act as a promising catalyst for light driven water oxidation.

show abstract

Section: Resultssupporting

confidence: 76%

Ruthenium Complexes of Substituted Terpyridine and Pyridyl-quinoline Based Ligands with Ancillary Ligands: Synthesis, Characterization, Electrochemical Study and DFT Calculation

et al. 2016

View full text Add to dashboard Cite

show abstract

“…The substitution of halide for water in these complexes results in an increase in the Ru d-orbital energy through π-donation from the halide, leading to the observed red shift. 11 The complexes 4a,b and 17 all contain the 2-(pyrid-2′-yl)-1,8-naphthyridine (pynap) ligand that is considerably more electronegative than bpy and hence the absorptions are shifted to lower energy (564, 568, and 573 nm). The complexes 5−11 all contain a 1,10-phenanthroline (phen) ligand and absorbances fall in the range of 481−523 nm.…”

Section: ■ Synthesis and Characterizationmentioning

confidence: 99%

Further Observations on Water Oxidation Catalyzed by Mononuclear Ru(II) Complexes

et al. 2012

View full text Add to dashboard Cite

A family of 28 mononuclear Ru(II) complexes have been prepared and characterized by (1)H NMR, electronic absorption, and cyclic voltammetry. These complexes are studied as catalysts for water oxidation. All the catalysts possess one tridentate ligand, closely related to 2,2';6,2''-terpyridine (tpy) and may be divided into two basic types. In the type-1 catalyst, the three remaining coordination sites are occupied by a bidentate closely related to 2,2'-bipyridine (bpy) and a monodentate halogen (Br, Cl, or I) or water molecule. In the type-2 catalyst, the three remaining coordination sites are occupied by two axial 4-picoline molecules and an equatorial halogen or water. In general the type-2 catalysts are more reactive than the type-1. The type-2 iodo-catalyst shows first-order behavior and, unlike the bromo- and chloro-catalysts, does not require water-halogen exchange to show good activity. The importance of steric strain and hindrance around the metal center is examined. The introduction of three t-butyl groups at the 4, 4', and 4'' positions of tpy sometimes improves catalyst activity, but the effect does not appear to be additive.

show abstract

“…The spectra of all the porphyrin-containing compounds are dominated by the strong Soret absorption band at around 420 nm as well as a maximum in the weaker Qband region at around 545 nm. [67] It seems that, in terms of spectral characteristics, the ruthenium and porphyrin fragments do not perturb each other significantly, resulting in an absorption spectrum that is essentially the sum of both chromophores (see Table 1). These features can also be observed for the single component [Ru(terpy)(bpy)-Cl](PF 6 ) in acetonitrile (acn, Table 1); [65,66] in dcm as solvent, an absorption maximum at 506 nm has been reported.…”

Section: Optical Propertiesmentioning

confidence: 99%

High‐Yielding Synthesis of a Hetero‐Pacman Compound and the Characterization of Intermediates and Side‐Products

et al. 2014

View full text Add to dashboard Cite

Through an optimized synthetic procedure, metalloligand 5, which features a hetero-Pacman scaffold comprising a porphyrin and a terpyridine moiety, has been assembled by a double Suzuki reaction. In a subsequent step, a rutheniumbipyridine fragment was introduced at the terpyridine coordination site of metalloligand 5 to form complex 6, which was fully characterized and its potential application in water oxidation catalysis tested. A number of side-products were iso-[a] Institute Scheme 1. Synthesis of compound 6 (mes = mesityl). Reagents and conditions: a) i. BuLi, B(OMe) 3 ; ii. H + /H 2 O; b) 2, [Pd(dppf)Cl 2 ], Rb 2 CO 3 , thf; c) CHCl 3 /MeOH; d) 4, [Pd(dppf)Cl 2 ], Rb 2 CO 3 , dioxane/water; e) i. [Ru(CH 3 CN) 2 (bpy)Cl 2 ], acetone; ii. NH 4 PF 6 /H 2 O.

show abstract

Electronic Structure and Spectroscopy of [Ru(tpy)₂]²⁺, [Ru(tpy)(bpy)(H₂O)]²⁺, and [Ru(tpy)(bpy)(Cl)]⁺

Cited by 99 publications

References 33 publications

Ruthenium Complexes of Substituted Terpyridine and Pyridyl-quinoline Based Ligands with Ancillary Ligands: Synthesis, Characterization, Electrochemical Study and DFT Calculation

Ruthenium Complexes of Substituted Terpyridine and Pyridyl-quinoline Based Ligands with Ancillary Ligands: Synthesis, Characterization, Electrochemical Study and DFT Calculation

Further Observations on Water Oxidation Catalyzed by Mononuclear Ru(II) Complexes

High‐Yielding Synthesis of a Hetero‐Pacman Compound and the Characterization of Intermediates and Side‐Products

Contact Info

Product

Resources

About