Back to Search
Start Over
Proton-Coupled Electron Transfer in a Ruthenium(II) Bipyrimidine Complex in Its Ground and Excited Electronic States.
- Source :
-
The journal of physical chemistry. A [J Phys Chem A] 2022 Jul 14; Vol. 126 (27), pp. 4349-4358. Date of Electronic Publication: 2022 Jun 29. - Publication Year :
- 2022
-
Abstract
- Proton-coupled electron transfer (PCET) was studied for the ground and excited electronic states of a [Ru(terpy)(bpm)(OH <subscript>2</subscript> )(PF <subscript>6</subscript> ) <subscript>2</subscript> ] complex, Ru-bpm . Cyclic voltammetry measurements show that the Ru(II)-aqua moiety undergoes PCET to form a Ru(IV)-oxo moiety in the anodic region, while the bpm ligand undergoes PCET to form bpmH <subscript>2</subscript> in the cathodic region. The photophysical behavior of Ru-bpm was studied using steady-state and femtosecond transient UV-vis absorption spectroscopy, coupled with density functional theory (DFT) calculations. The lowest-lying excited state of Ru-bpm is described as a (Ru → bpm) metal-to-ligand charge-transfer (MLCT) state, while the metal-centered (MC) excited state was found computationally to be close in energy to the lowest-energy bright MLCT state (MC state was 0.16 eV above the MLCT state). The excited-state kinetics of Ru-bpm were found via transient absorption spectroscopy to be short-lived and were fit well to a biexponential function with lifetimes τ <subscript>1</subscript> = 4 ps and τ <subscript>2</subscript> = 65 ps in aqueous solution. Kinetic isotope effects of 1.75 (τ <subscript>1</subscript> ) and 1.61 (τ <subscript>2</subscript> ) were observed for both decay components, indicating that the solvent plays an important role in the excited-state dynamics of Ru-bpm . Based on the pH-dependent studies and the results from prior studies of similar Ru-complexes, we hypothesize that the <superscript>3</superscript> MLCT state forms an excited-state hydrogen-bond adduct with the solvent molecules and that this process occurs with a 4 ps lifetime. The formation of such a hydrogen-bond complex is consistent with the electronic density accumulation at the peripheral N atoms of the bpm moiety in the <superscript>3</superscript> MLCT state. The hydrogen-bonded state <superscript>3</superscript> MLCT decays to the ground state with a 65 ps lifetime. Such a short lifetime is likely associated with the efficient vibrational energy transfer from the <superscript>3</superscript> MLCT state to the solvent.
- Subjects :
- Electronics
Electrons
Ligands
Protons
Solvents
Ruthenium chemistry
Subjects
Details
- Language :
- English
- ISSN :
- 1520-5215
- Volume :
- 126
- Issue :
- 27
- Database :
- MEDLINE
- Journal :
- The journal of physical chemistry. A
- Publication Type :
- Academic Journal
- Accession number :
- 35766591
- Full Text :
- https://doi.org/10.1021/acs.jpca.2c02255