Electron delocalization in a rigid cofacial naphthalene-1,8

4,5- bis(dicarboximide) dimer

Yilei Wu, Marco Frasconi, Daniel M. Gardner, Paul R. McGonigal, Severin T. Schneebeli, Michael R Wasielewski, J. Fraser Stoddart

Research output: Contribution to journalArticle

56 Citations (Scopus)

Abstract

Investigating through-space electronic communication between discrete cofacially oriented aromatic π-systems is fundamental to understanding assemblies as diverse as double-stranded DNA, organic photovoltaics and thin-film transistors. A detailed understanding of the electronic interactions involved rests on making the appropriate molecular compounds with rigid covalent scaffolds and π-π distances in the range of ca. 3.5 Å. Reported herein is an enantiomeric pair of doubly-bridged naphthalene-1,8:4,5- bis(dicarboximide) (NDI) cyclophanes and the characterization of four of their electronic states, namely 1) the ground state, 2) the exciton coupled singlet excited state, 3) the radical anion with strong through-space interactions between the redox-active NDI molecules, and 4) the diamagnetic diradical dianion using UV/Vis/NIR, EPR and ENDOR spectroscopies in addition to X-ray crystallography. Despite the unfavorable Coulombic repulsion, the singlet diradical dianion dimer of NDI shows a more pronounced intramolecular π-π stacking interaction when compared with its neutral analog. Two are better than one: A doubly-bridged naphthalene diimide (NDI) cyclophane has been synthesized. It shows efficient π-orbital overlap between two rigid cofacial NDI units. The resulting through-space electronic delocalization in the neutral as well as reduced states induces emergent photophysical, electrochemical, and magnetic properties both in solution and in the solid phase.

Original languageEnglish
Pages (from-to)9476-9481
Number of pages6
JournalAngewandte Chemie - International Edition
Volume53
Issue number36
DOIs
Publication statusPublished - 2014

Fingerprint

Naphthalene
Dimers
Electrons
X ray crystallography
X Ray Crystallography
Electron Spin Resonance Spectroscopy
Electronic states
Thin film transistors
Electrochemical properties
Excited states
Scaffolds
Ground state
Oxidation-Reduction
Anions
Paramagnetic resonance
Spectrum Analysis
Magnetic properties
Excitons
naphthalene-1,8:4,5-bis(dicarboximide)
naphthalenediimide

Keywords

  • cyclophane
  • excimer emission
  • mixed-valence compounds
  • radical anion dimer
  • π-electron delocalization

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Medicine(all)

Cite this

Electron delocalization in a rigid cofacial naphthalene-1,8 : 4,5- bis(dicarboximide) dimer. / Wu, Yilei; Frasconi, Marco; Gardner, Daniel M.; McGonigal, Paul R.; Schneebeli, Severin T.; Wasielewski, Michael R; Stoddart, J. Fraser.

In: Angewandte Chemie - International Edition, Vol. 53, No. 36, 2014, p. 9476-9481.

Research output: Contribution to journalArticle

Wu, Yilei ; Frasconi, Marco ; Gardner, Daniel M. ; McGonigal, Paul R. ; Schneebeli, Severin T. ; Wasielewski, Michael R ; Stoddart, J. Fraser. / Electron delocalization in a rigid cofacial naphthalene-1,8 : 4,5- bis(dicarboximide) dimer. In: Angewandte Chemie - International Edition. 2014 ; Vol. 53, No. 36. pp. 9476-9481.
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