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Microsecond (MLCT)-M-3 excited state lifetimes in bis-tridentate Ru(II)-complexes: significant reductions of non-radiative rate constants
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.ORCID iD: 0000-0002-6931-1128
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
2017 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 46, no 39, 13314-13321 p.Article in journal (Refereed) Published
Abstract [en]

In this paper we report the photophysical properties of a series of bis-tridentate Ru-II-complexes, based on the dqp-ligand (dqp = 2,6-di(quinolin-8-yl) pyridine), which display several microsecond long excited state lifetimes for triplet metal-to-ligand charge transfer ((MLCT)-M-3) at room temperature. Temperature dependence of the excited state lifetimes for [Ru(dqp)(2)](2+) and [Ru(dqp)(ttpy)](2+) (ttpy = 4'-tolyl-2,2': 6', 2 ''-terpyridine) is reported and radiative and non-radiative rate constants for the whole series are reported and discussed. We can confirm previous assumptions that the near-octahedricity of the bis-dqp complexes dramatically slows down activated decay at room temperature, as compared to most other and less long-lived bis-tridentate RuII-complexes, such as [Ru(tpy)(2)](2+) with tau = 0.25 ns at room temperature (tpy = 2,2': 6', 2 ''-terpyridine). Moreover, the direct non-radiative decay to the ground state is comparatively slow for similar to 700 nm room-temperature emission when considering the energy-gap law. Analysis of the 77 K emission spectra suggests that this effect is not primarily due to smaller excited state distortion than that for comparable complexes. Instead, an analysis of the photophysical parameters suggests a weaker singlet-triplet mixing in the MLCT state, which slows down both radiative and non-radiative decay.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY , 2017. Vol. 46, no 39, 13314-13321 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-337326DOI: 10.1039/c7dt02437aISI: 000412765000018PubMedID: 28799607OAI: oai:DiVA.org:uu-337326DiVA: diva2:1171453
Funder
Swedish Energy AgencyKnut and Alice Wallenberg Foundation
Available from: 2018-01-08 Created: 2018-01-08 Last updated: 2018-01-08Bibliographically approved

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