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Kohler L, Hayes D, Hong J, et al. Synthesis, structure, ultrafast kinetics, and light-induced dynamics of CuHETPHEN chromophores. Dalton Trans. 2016;45(24):9871-83doi: 10.1039/c6dt00324a.
Kohler, L., Hayes, D., Hong, J., Carter, T. J., Shelby, M. L., Fransted, K. A., Chen, L. X., & Mulfort, K. L. (2016). Synthesis, structure, ultrafast kinetics, and light-induced dynamics of CuHETPHEN chromophores. Dalton transactions (Cambridge, England : 2003), 45(24), 9871-83. https://doi.org/10.1039/c6dt00324a
Kohler, Lars, et al. "Synthesis, structure, ultrafast kinetics, and light-induced dynamics of CuHETPHEN chromophores." Dalton transactions (Cambridge, England : 2003) vol. 45,24 (2016): 9871-83. doi: https://doi.org/10.1039/c6dt00324a
Kohler L, Hayes D, Hong J, Carter TJ, Shelby ML, Fransted KA, Chen LX, Mulfort KL. Synthesis, structure, ultrafast kinetics, and light-induced dynamics of CuHETPHEN chromophores. Dalton Trans. 2016 Jun 14;45(24):9871-83. doi: 10.1039/c6dt00324a. PMID: 26924711.
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Dalton Trans. 2016 Jun 14;45(24):9871-83. doi: 10.1039/c6dt00324a.

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

Dalton transactions (Cambridge, England : 2003)

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

Affiliations

  1. Division of Chemical Sciences and Engineering, Argonne National Laboratory, 9700 South Cass Ave, Argonne, IL 60439, USA. [email protected].
  2. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, USA.
  3. Division of Chemical Sciences and Engineering, Argonne National Laboratory, 9700 South Cass Ave, Argonne, IL 60439, USA. [email protected] and Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, USA.

PMID: 26924711 DOI: 10.1039/c6dt00324a

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.

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