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Title: Ligand Mediation of Vectorial Charge Transfer in Cu(I)diimine Chromophore–Acceptor Dyads

In this paper, 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. Finally, 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.
Authors:
ORCiD logo [1] ;  [1] ; ORCiD logo [2] ; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Division of Chemical Sciences and Engineering
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Division of Chemical Sciences and Engineering; Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 8; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1461458