Ligand Mediation of Vectorial Charge Transfer in Cu(I)diimine Chromophore-Acceptor Dyads

Dugan Hayes, Lars Kohler, Lin X. Chen, Karen L. Mulfort*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

In this work, we present the photoinduced charge separation dynamics of four molecular dyads composed of heteroleptic Cu(I)bis(phenanthroline) chromophores linked directly to the common electron acceptor naphthalene diimide. The dyads were designed to allow us to (1) detect any kinetic preference for directionality during photoinduced electron transfer across the heteroleptic complex and (2) probe the influence of excited-state flattening on intramolecular charge separation. Singular value decomposition of ultrafast optical transient absorption spectra demonstrates that charge transfer occurs with strong directional preference, and charge separation occurs up to 35 times faster when the acceptor is linked to the sterically blocking ligand. Further, the charge-separated state in these dyads is stabilized by polar solvents, resulting in dramatically longer lifetimes for dyads with minimal substitution about the Cu(I) center. This unexpected but exciting observation suggests a new approach to the design of Cu(I)bis(phenanthroline) chromophores that can support long-lived vectorial charge separation.

Original languageEnglish (US)
Pages (from-to)2070-2076
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume9
Issue number8
DOIs
StatePublished - Apr 19 2018

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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