Electron Hopping and Charge Separation within a Naphthalene-1,4: 5,8-bis(dicarboximide) Chiral Covalent Organic Cage

Tomáš Šolomek, Natalia E. Powers-Riggs, Yi Lin Wu, Ryan M. Young, Matthew D. Krzyaniak, Noah E. Horwitz, Michael R Wasielewski

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

We present the stereoselective synthesis of a chiral covalent organic cage consisting of three redox-active naphthalene-1,4:5,8-bis(dicarboximide) (NDI) units by dynamic imine chemistry. Single crystal X-ray diffraction analysis shows that host-guest interactions and racemic cocrystallization allow for controlling the solid state structure. Electronic interactions between the NDI units probed by absorption and circular dichroism spectroscopies, electrochemistry and theoretical calculations are shown to be weak. Photoexcitation of NDI leads to intracage charge separation with a longer lifetime than observed in the corresponding monomeric NDI and dimeric NDI cyclophane imines. The EPR spectrum of the singly reduced cage shows that the electron is localized on a single NDI unit at ambient temperatures and transitions to rapid hopping among all three NDI units upon heating to 350 K. Dynamic covalent chemistry thus promises rapid access to covalent organic cages with well-defined architectures to study charge accumulation and electron transport phenomena.

Original languageEnglish
Pages (from-to)3348-3351
Number of pages4
JournalJournal of the American Chemical Society
Volume139
Issue number9
DOIs
Publication statusPublished - Mar 8 2017

Fingerprint

Imines
Naphthalene
Electrons
Circular dichroism spectroscopy
Electrochemistry
Transition Temperature
Photoexcitation
Electron Transport
Circular Dichroism
X-Ray Diffraction
Heating
X ray diffraction analysis
Oxidation-Reduction
Paramagnetic resonance
Spectrum Analysis
Single crystals
Temperature
naphthalene

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Electron Hopping and Charge Separation within a Naphthalene-1,4 : 5,8-bis(dicarboximide) Chiral Covalent Organic Cage. / Šolomek, Tomáš; Powers-Riggs, Natalia E.; Wu, Yi Lin; Young, Ryan M.; Krzyaniak, Matthew D.; Horwitz, Noah E.; Wasielewski, Michael R.

In: Journal of the American Chemical Society, Vol. 139, No. 9, 08.03.2017, p. 3348-3351.

Research output: Contribution to journalArticle

Šolomek, Tomáš ; Powers-Riggs, Natalia E. ; Wu, Yi Lin ; Young, Ryan M. ; Krzyaniak, Matthew D. ; Horwitz, Noah E. ; Wasielewski, Michael R. / Electron Hopping and Charge Separation within a Naphthalene-1,4 : 5,8-bis(dicarboximide) Chiral Covalent Organic Cage. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 9. pp. 3348-3351.
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