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Issue 39, 2017
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Microsecond 3MLCT excited state lifetimes in bis-tridentate Ru(II)-complexes: significant reductions of non-radiative rate constants

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Abstract

In this paper we report the photophysical properties of a series of bis-tridentate RuII-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 (3MLCT) 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 τ = 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 ∼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.

Graphical abstract: Microsecond 3MLCT excited state lifetimes in bis-tridentate Ru(ii)-complexes: significant reductions of non-radiative rate constants

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Publication details

The article was received on 05 Jul 2017, accepted on 27 Jul 2017 and first published on 27 Jul 2017


Article type: Paper
DOI: 10.1039/C7DT02437A
Citation: Dalton Trans., 2017,46, 13314-13321
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    Microsecond 3MLCT excited state lifetimes in bis-tridentate Ru(II)-complexes: significant reductions of non-radiative rate constants

    M. Abrahamsson, H. Becker and L. Hammarström, Dalton Trans., 2017, 46, 13314
    DOI: 10.1039/C7DT02437A

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