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Issue 24, 2016
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Synthesis, structure, ultrafast kinetics, and light-induced dynamics of CuHETPHEN chromophores

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Abstract

Five heteroleptic Cu(I)bis(phenanthroline) chromophores with distinct variation in the steric bulk at the 2,9-phenanthroline position were synthesized using the HETPHEN method, and their ground and excited state properties are described. Analysis of the crystal structures reveals a significant distortion from tetrahedral geometry around the Cu(I) centre which is attributed to favourable aromatic interactions between the two phenanthroline ligands. Ultrafast and nanosecond transient optical spectroscopies reveal that the excited state lifetime can be tuned across two orders of magnitude up to 74 nanoseconds in acetonitrile by changing the 2,9-substituent from hydrogen to sec-butyl. X-ray transient absorption spectroscopy at the Cu K-edge confirmed Cu(I) oxidation to Cu(II) and revealed a decrease of the Cu–N bond lengths in the excited state. The ground and excited state characterization presented here will guide the integration of CuHETPHEN chromophores into complex electron donor–acceptor architectures.

Graphical abstract: Synthesis, structure, ultrafast kinetics, and light-induced dynamics of CuHETPHEN chromophores

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Publication details

The article was received on 22 Jan 2016, accepted on 22 Feb 2016 and first published on 29 Feb 2016


Article type: Paper
DOI: 10.1039/C6DT00324A
Citation: Dalton Trans., 2016,45, 9871-9883
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    Synthesis, structure, ultrafast kinetics, and light-induced dynamics of CuHETPHEN chromophores

    L. Kohler, D. Hayes, J. Hong, T. J. Carter, M. L. Shelby, K. A. Fransted, L. X. Chen and K. L. Mulfort, Dalton Trans., 2016, 45, 9871
    DOI: 10.1039/C6DT00324A

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