Spectroscopy and photophysics of chloro-bis-bipyridyl complexes of ruthenium(II) with pyridine ligands

Литке, С. В.; Mezentseva, T. V.; Lyalin, G. N.; Еrshov, A. Yu.

doi:10.1134/1.1635477

Cited by 10 publications

(18 citation statements)

References 15 publications

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“…A similar pattern exists in comparing cis -[Ru(bpy) 2 (py)Cl] + , cis -[Ru(bpy) 2 (py) 2 ] 2+ , and cis -[Ru(bpy) 2 (py)NO 2 l] + (our measurements, unpublished, and ref ). The molar extinction coefficients at the maximum for the low-energy visible absorption bands are approximately equal (∼0.8 × 10 4 m –1 cm –1 ) and values of k r × 10 –4 (in alcoholic glass at 77 K) increase from 2 to 4 and to 5 s –1 by exchanging a donor ligand Cl – with acceptor ligands py and NO 2 – , respectively.…”

Section: Discussionsupporting

confidence: 84%

Deactivation Pathways for Metal-to-Ligand Charge-Transfer Excited States of Ruthenium Polypyridyl Complexes with Triphenylphosphine as a Ligand

2011

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Emission, excitation spectra, quantum yields, and emission lifetimes are reported for the mixed-ligand, bis(2.2'-bipyridine)ruthenium(II) complexes, cis-[Ru(bpy)(2)(PPh(3))X](n+) with X = Cl(-), Br(-), CN(-), and NO(2)(-) (n = 1) and pyridine (py), 4-aminopyridine (NH(2)py), 4,4'- bipyridine (4,4'-bpy), NH(3), and MeCN (n = 2) in EtOH-MeOH, 4:1 (v:v), at 77 K. Radiative, k(r), and nonradiative, k(nr), decay rate constants were determined for the series of complexes, and a linear dependence of ln k(nr) on E(00), with E(00) being the 0-0 energy gap determined by emission spectral fitting, was obtained with a slope of -(0.6 ± 0.1) × 10(-3). On the basis of emission quantum yields and apparent k(r) values, possible metal-to-ligand charge-transfer (MLCT) deactivation by direct population of excited (1)dd states from initially excited (1)MLCT states is discussed.

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Section: Discussionsupporting

confidence: 84%

Deactivation Pathways for Metal-to-Ligand Charge-Transfer Excited States of Ruthenium Polypyridyl Complexes with Triphenylphosphine as a Ligand

2011

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“…It is also interesting to consider the role of the nonchromophoric ligand X in the series cis -[Ru(bpy) 2 (L)X] n + with data available from earlier results , on 4-substituted py derivatives as ligands (L) X = Cl – and PPh 3 . Example absorption spectra are shown in alcohol in Figure for L = bipy and X = NO 2 – , Cl – , and PPh 3 .…”

Section: Discussionmentioning

confidence: 99%

“…49−56 We have also investigated the photophysical properties of these complexes in EtOH−MeOH glasses at low temperatures (77 K), where complications from thermal population and decay through dd states is typically unimportant. 57,58 In detailed studies on chloro complexes of the type cis-[Ru(bpy) 2 (L)Cl] + , with pyrazine and 4-substituted derivatives of pyridine (py) as ligands (L), a linear correlation between the E 00 energy of the lowest-energy 3 MLCT {[d π (Ru) → π*(bpy)]} excited states and pK a (L−H + ) for the free ligands was found. In this series, complexes with L as a strong electrondonating N-donor ligand have lower E 00 energies than those with π-acceptor substituents.…”

Section: ■ Introductionmentioning

confidence: 99%

“…With the goal of understanding the role of dd states in deactivation pathways for the MLCT excited states in complexes of this type, we have studied systematically the electronic structure and photochemistry of cis -[Ru(bpy) 2 (L)X] n + complexes in solution. − We have also investigated the photophysical properties of these complexes in EtOH–MeOH glasses at low temperatures (77 K), where complications from thermal population and decay through dd states is typically unimportant. , …”

Section: Introductionmentioning

confidence: 99%

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Photophysics of Bis-bipyridyl Nitro Complexes of Ruthenium(II) with Pyridine Ligands: Substituent Effects

2014

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Emission, excitation spectra, quantum yields, and emission lifetimes are reported for the mixed ligand, bis-(2,2'-bipyridine)ruthenium(II) complexes cis-[Ru(bpy)2(L)(NO2)](+) with 4-substituted pyridines as ligands L [isonicotinamide (isnc), 4,4'-bipyridine (bipy), pyridine (py), 4-phenylpyridine (phpy), 1,2-bis(4-pyridyl)ethane (bpa), 4-picoline (mepy), 4-aminopyridine (apy), and 4-dimethylaminopyridine (ampy)] in EtOH-MeOH, 4:1 (V:V), at 77 K. Radiative, k(r), and nonradiative, k(nr), decay rate constants were determined for the series of complexes, and a linear dependence of ln k(nr) on E00, with E00 as the 0-0 energy gap determined by emission spectral fitting, was obtained with a slope of -(3.35 ± 0.23) × 10(-4) cm(-1). A linear correlation of E00 for cis-[Ru(bpy)2(L)(NO2)](+) complexes and Hammett substituent constant σ(p) is found.

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“…22 The peak at 360 nm is an intraligand π-π* bipy transition observed in particular when the Ru-atom has two bipy ligands and a monocoordinated pyridine-based ligand. 24 The lack of this peak after the BZ reaction demonstrates the removal of the 4-pyridinecarboxylic acid ligands in 2. Because the E 0 of 2 is similar to that of ] was increased by 300 mM.…”

Section: Resultsmentioning

confidence: 99%

Terpyridine- and Bipyridine-Based Ruthenium Complexes as Catalysts for the Belousov−Zhabotinsky Reaction

Delgado

Zhang

et al. 2011

J. Phys. Chem. A

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We report the successful use of Ru(II)(terpy)(2) (1, terpy = 2,2':6',2''-terpyridine) as a catalyst in the Belousov-Zhabotinsky (BZ) oscillating chemical reaction. We also examine several additional Ru(II) complexes, Ru(II)(bipy)(2)(L')(2) (2, L' = 4-pyridinecarboxylic acid; bipy = 2,2'-bipyridine) and Ru(II)(bipy)(2)(L'') (3, L'' = 4,4'-dicarboxy-2,2'-bipy; 4, L'' = N-allyl-4'-methyl-[2,2'-bipy]-4-carboxamide; 5, L'' = bipy), for catalyzing the BZ reaction. While 2 is unable to trigger BZ oscillations, probably because of the rapid loss of L' in a BZ solution, the other bipyridine-based Ru(II)-complexes can catalyze the BZ reaction, although their catalytic activity is adversely affected by slow ligand substitution in a BZ solution. Nevertheless, the successfully tested Ru(II)(terpy)(2) and Ru(II)(bipy)(2)(L'') catalysts may provide useful building blocks for complex functional macromolecules.

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Spectroscopy and photophysics of chloro-bis-bipyridyl complexes of ruthenium(II) with pyridine ligands

Cited by 10 publications

References 15 publications

Deactivation Pathways for Metal-to-Ligand Charge-Transfer Excited States of Ruthenium Polypyridyl Complexes with Triphenylphosphine as a Ligand

Deactivation Pathways for Metal-to-Ligand Charge-Transfer Excited States of Ruthenium Polypyridyl Complexes with Triphenylphosphine as a Ligand

Photophysics of Bis-bipyridyl Nitro Complexes of Ruthenium(II) with Pyridine Ligands: Substituent Effects

Terpyridine- and Bipyridine-Based Ruthenium Complexes as Catalysts for the Belousov−Zhabotinsky Reaction

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