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

Lars Kohler, Dugan Hayes, Jiyun Hong, Tyler J. Carter, Megan L. Shelby, Kelly A. Fransted, Lin X. Chen, Karen L. Mulfort*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

22 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)9871-9883
Number of pages13
JournalDalton Transactions
Volume45
Issue number24
DOIs
StatePublished - 2016

ASJC Scopus subject areas

  • Inorganic Chemistry

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