Research output: Contribution to journal › Article › peer-review
Electronically exited states in triphenylphosphine complexes of Ruthenium (II): TD DFT study. / Krauklis, Irina V. ; Reshetova, Kristina I. ; Podkopaeva, Oksana Yu. ; Chizhov, Yuri V. .
In: Journal of Photochemistry and Photobiology A: Chemistry, Vol. 354, 2018, p. 112-118.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Electronically exited states in triphenylphosphine complexes of Ruthenium (II): TD DFT study
AU - Krauklis, Irina V.
AU - Reshetova, Kristina I.
AU - Podkopaeva, Oksana Yu.
AU - Chizhov, Yuri V.
PY - 2018
Y1 - 2018
N2 - Singlet and triplet electronically exited states (EES) of the luminescent and photoactive complexes [Ru (bpy)2(PPh3) (L)]+2, where bpy is 2,20 - bipyridyl, L is 4-aminopyridine, pyridine (py), or 4,40 - bipyridyl (bipy) are studied within TDDFT/B3LYP/[6-31G(d) + LanL2DZ(Ru)] method in the energy region of 2.2 eV 4.5 eV. We revealed the nature of more than 70 EES and constructed a series of multi-level schemes of the EE states, taking into account 3 dd levels of Ru (II) and metal-to-ligand charge-transfer states of pyridine ligands (MLCT(L)). These schemes gave us the opportunity to evaluate the activation energy of 3 dd-states of Ru (II) ion and to explain the weak luminescence of triphenylphosphine complexes of Ruthenium (II) (TPRC) at room temperature. Besides, we discovered that the emission energy (Eem) of the principal luminescent transition 3 MLCT!1 GS of the complexes studied depends linearly on the effective charge on the nitrogen atom (Q(N4)) of the coordinated pyridyl ligand. The electronic absorption spectra of TPRC are calculated and interpreted within TD DFT, and the energy of luminescenttransition (ET-S) from the lowest triplet 3 MLCT to the ground state for all TPRC under study is evaluated. It is shown that the variation of pyridine ligands (L) from electron donors to electron acceptors results in the hypsochromic shift of ET-S, which is in good agreement with the experimental data.
AB - Singlet and triplet electronically exited states (EES) of the luminescent and photoactive complexes [Ru (bpy)2(PPh3) (L)]+2, where bpy is 2,20 - bipyridyl, L is 4-aminopyridine, pyridine (py), or 4,40 - bipyridyl (bipy) are studied within TDDFT/B3LYP/[6-31G(d) + LanL2DZ(Ru)] method in the energy region of 2.2 eV 4.5 eV. We revealed the nature of more than 70 EES and constructed a series of multi-level schemes of the EE states, taking into account 3 dd levels of Ru (II) and metal-to-ligand charge-transfer states of pyridine ligands (MLCT(L)). These schemes gave us the opportunity to evaluate the activation energy of 3 dd-states of Ru (II) ion and to explain the weak luminescence of triphenylphosphine complexes of Ruthenium (II) (TPRC) at room temperature. Besides, we discovered that the emission energy (Eem) of the principal luminescent transition 3 MLCT!1 GS of the complexes studied depends linearly on the effective charge on the nitrogen atom (Q(N4)) of the coordinated pyridyl ligand. The electronic absorption spectra of TPRC are calculated and interpreted within TD DFT, and the energy of luminescenttransition (ET-S) from the lowest triplet 3 MLCT to the ground state for all TPRC under study is evaluated. It is shown that the variation of pyridine ligands (L) from electron donors to electron acceptors results in the hypsochromic shift of ET-S, which is in good agreement with the experimental data.
KW - Photoactive triphenylphosphine Ruthenium(II) complexes
KW - Electronically exited states
KW - TDDFT
KW - Photoactive triphenylphosphine Ruthenium (II) complexes Electronically exited states TDDFT
M3 - Article
VL - 354
SP - 112
EP - 118
JO - Journal of Photochemistry and Photobiology A: Chemistry
JF - Journal of Photochemistry and Photobiology A: Chemistry
SN - 1010-6030
ER -
ID: 9139217