Probing metal-to-ligand charge transfer transitions in ruthenium complexes by quantitative two-photon absorption spectroscopy

Stark, Charles W.; Rammo, Matt; Pahapill, Jüri; Mikhaylov, Alexander; Rebane, Aleksander

doi:10.1117/12.2290363

Cited by 2 publications

(2 citation statements)

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“…Limited π-conjugation together with inter-annular twisting within the π-extended bipyridine ligands resulted in relatively modest TPA properties [ 45 ]. Recent studies demonstrate the importance of the geometry in the first sphere around the ruthenium core [ 46 ], which is consistent with the idea that an octupolar D 3 symmetry should be approached to achieve high cross-section values.…”

Section: Introductionsupporting

confidence: 73%

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Two-Photon Absorption Cooperative Effects within Multi-Dipolar Ruthenium Complexes: The Decisive Influence of Charge Transfers

et al. 2022

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One- and two-photon characterizations of a series of hetero- and homoleptic [RuL3-n(bpy)n]2+ (n = 0, 1, 2) complexes carrying bipyridine π-extended ligands (L), have been carried out. These π-extended D−π−A−A−π−D-type ligands (L), where the electron donor units (D) are based on diphenylamine, carbazolyl, or fluorenyl units, have been designed to modulate the conjugation extension and the donating effect. Density functional theory calculations were performed in order to rationalize the observed spectra. Calculations show that the electronic structure of the π-extended ligands has a pronounced effect on the composition of HOMO and LUMO and on the metallic contribution to frontier MOs, resulting in strikingly different nonlinear properties. This work demonstrates that ILCT transitions are the keystone of one- and two-photon absorption bands in the studied systems and reveals how much MLCT and LLCT charge transfers play a decisive role on the two-photon properties of both hetero- and homoleptic ruthenium complexes through cooperative or suppressive effects.

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Section: Introductionsupporting

confidence: 73%

“…Evolution of intrinsic TPA cross-sections as a function of the number of ligands, L T ( a ), L C ( b ), and L F ( c ), in [RuL 3-n (bpy) n ] 2+ complexes. Ru(bpy) 3 2+ acts as a reference ( n = 0) [ 46 ].…”

Section: Figures Scheme and Tablesmentioning

confidence: 99%

Two-Photon Absorption Cooperative Effects within Multi-Dipolar Ruthenium Complexes: The Decisive Influence of Charge Transfers

et al. 2022

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Polypyridyl Ruthenium Complexes: Versatile Tools for Linear and Non-Linear Optics

Durand

Savel

Akdas-Kiliç

et al. 2019

2019 21st International Conference on Transparent Optical Networks (ICTON)

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Coordination complexes have been attracting considerable interest due to their potential nonlinear optical (NLO) properties and applications in optoelectronic and photonic devices. Incorporation of metal atoms into πconjugated systems allows many variables to be adjusted, such as the nature of ligands and metal ions as well as the symmetry of the complexes. In this paper, new ruthenium(II) complexes of formula [Ru(bpy) 2 (L)][PF 6 ] and [Ru (L) 3 ][PF 6 ] 2 are reported. We studied the influence of the nature of ligands, structural features and symmetry of these complexes on their two-photon absorption properties to provide useful physical and chemical insights for similar ruthenium complexes.

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Probing metal-to-ligand charge transfer transitions in ruthenium complexes by quantitative two-photon absorption spectroscopy

Cited by 2 publications

References 47 publications

Two-Photon Absorption Cooperative Effects within Multi-Dipolar Ruthenium Complexes: The Decisive Influence of Charge Transfers

Two-Photon Absorption Cooperative Effects within Multi-Dipolar Ruthenium Complexes: The Decisive Influence of Charge Transfers

Polypyridyl Ruthenium Complexes: Versatile Tools for Linear and Non-Linear Optics

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