Spectroscopic signatures of ligand field states in {RuII(imine)} complexes
Ligand field (LF) states have been present in discussions on the photophysics and photochemistry of ruthenium-iminic chromophores for decades, although there is very little documented direct evidence of them. We studied the picosecond transient absorption (TA) spectroscopy of four {RuII(imine)} comp...
Guardado en:
| Autores principales: | , , , , , |
|---|---|
| Formato: | JOUR |
| Materias: | |
| Acceso en línea: | http://hdl.handle.net/20.500.12110/paper_14779226_v45_n13_p5464_Cadranel |
| Aporte de: |
| id |
todo:paper_14779226_v45_n13_p5464_Cadranel |
|---|---|
| record_format |
dspace |
| spelling |
todo:paper_14779226_v45_n13_p5464_Cadranel2023-10-03T16:19:16Z Spectroscopic signatures of ligand field states in {RuII(imine)} complexes Cadranel, A. Pieslinger, G.E. Tongying, P. Kuno, M.K. Baraldo, L.M. Hodak, J.H. Chromophores Ligands Nitrogen compounds Ruthenium Spectroelectrochemistry Absorption features Donor and acceptor Ligand field Polypyridines Spectroelectrochemical technique Spectroscopic evidence Spectroscopic signatures Transient absorption Absorption spectroscopy Ligand field (LF) states have been present in discussions on the photophysics and photochemistry of ruthenium-iminic chromophores for decades, although there is very little documented direct evidence of them. We studied the picosecond transient absorption (TA) spectroscopy of four {RuII(imine)} complexes that respond to the formula trans-[Ru(L)4(X)2], where L is either pyridine (py) or 4-methoxypyridine (MeOpy) and X is either cyanide or thiocyanate. Dicyano compounds behave as most ruthenium polypyridines and their LF states remain silent. In contrast, in the dithiocyanate complexes we found clear spectroscopic evidence of the participation of LF states in the MLCT decay pathway. These states are of donor and acceptor character simultaneously and this is manifested in the presence of MLCT and LMCT transient absorption bands of similar energy. Spectroelectrochemical techniques supported the interpretation of the absorption features of MLCT states, and DFT methods helped to assign their spectroscopic signatures and provided strong evidence on the nature of LF states. © 2016 The Royal Society of Chemistry. Fil:Cadranel, A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Baraldo, L.M. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Hodak, J.H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_14779226_v45_n13_p5464_Cadranel |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Chromophores Ligands Nitrogen compounds Ruthenium Spectroelectrochemistry Absorption features Donor and acceptor Ligand field Polypyridines Spectroelectrochemical technique Spectroscopic evidence Spectroscopic signatures Transient absorption Absorption spectroscopy |
| spellingShingle |
Chromophores Ligands Nitrogen compounds Ruthenium Spectroelectrochemistry Absorption features Donor and acceptor Ligand field Polypyridines Spectroelectrochemical technique Spectroscopic evidence Spectroscopic signatures Transient absorption Absorption spectroscopy Cadranel, A. Pieslinger, G.E. Tongying, P. Kuno, M.K. Baraldo, L.M. Hodak, J.H. Spectroscopic signatures of ligand field states in {RuII(imine)} complexes |
| topic_facet |
Chromophores Ligands Nitrogen compounds Ruthenium Spectroelectrochemistry Absorption features Donor and acceptor Ligand field Polypyridines Spectroelectrochemical technique Spectroscopic evidence Spectroscopic signatures Transient absorption Absorption spectroscopy |
| description |
Ligand field (LF) states have been present in discussions on the photophysics and photochemistry of ruthenium-iminic chromophores for decades, although there is very little documented direct evidence of them. We studied the picosecond transient absorption (TA) spectroscopy of four {RuII(imine)} complexes that respond to the formula trans-[Ru(L)4(X)2], where L is either pyridine (py) or 4-methoxypyridine (MeOpy) and X is either cyanide or thiocyanate. Dicyano compounds behave as most ruthenium polypyridines and their LF states remain silent. In contrast, in the dithiocyanate complexes we found clear spectroscopic evidence of the participation of LF states in the MLCT decay pathway. These states are of donor and acceptor character simultaneously and this is manifested in the presence of MLCT and LMCT transient absorption bands of similar energy. Spectroelectrochemical techniques supported the interpretation of the absorption features of MLCT states, and DFT methods helped to assign their spectroscopic signatures and provided strong evidence on the nature of LF states. © 2016 The Royal Society of Chemistry. |
| format |
JOUR |
| author |
Cadranel, A. Pieslinger, G.E. Tongying, P. Kuno, M.K. Baraldo, L.M. Hodak, J.H. |
| author_facet |
Cadranel, A. Pieslinger, G.E. Tongying, P. Kuno, M.K. Baraldo, L.M. Hodak, J.H. |
| author_sort |
Cadranel, A. |
| title |
Spectroscopic signatures of ligand field states in {RuII(imine)} complexes |
| title_short |
Spectroscopic signatures of ligand field states in {RuII(imine)} complexes |
| title_full |
Spectroscopic signatures of ligand field states in {RuII(imine)} complexes |
| title_fullStr |
Spectroscopic signatures of ligand field states in {RuII(imine)} complexes |
| title_full_unstemmed |
Spectroscopic signatures of ligand field states in {RuII(imine)} complexes |
| title_sort |
spectroscopic signatures of ligand field states in {ruii(imine)} complexes |
| url |
http://hdl.handle.net/20.500.12110/paper_14779226_v45_n13_p5464_Cadranel |
| work_keys_str_mv |
AT cadranela spectroscopicsignaturesofligandfieldstatesinruiiiminecomplexes AT pieslingerge spectroscopicsignaturesofligandfieldstatesinruiiiminecomplexes AT tongyingp spectroscopicsignaturesofligandfieldstatesinruiiiminecomplexes AT kunomk spectroscopicsignaturesofligandfieldstatesinruiiiminecomplexes AT baraldolm spectroscopicsignaturesofligandfieldstatesinruiiiminecomplexes AT hodakjh spectroscopicsignaturesofligandfieldstatesinruiiiminecomplexes |
| _version_ |
1807316027283865600 |