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 language | English (US) |
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Pages (from-to) | 9476-9481 |
Number of pages | 6 |
Journal | Angewandte Chemie - International Edition |
Volume | 53 |
Issue number | 36 |
DOIs | |
State | Published - Sep 1 2014 |
Keywords
- cyclophane
- excimer emission
- mixed-valence compounds
- radical anion dimer
- π-electron delocalization
ASJC Scopus subject areas
- General Chemistry
- Catalysis
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CCDC 994128: Experimental Crystal Structure Determination
Wu, Y. (Contributor), Frasconi, M. (Contributor), Gardner, D. M. (Contributor), McGonigal, P. R. (Contributor), Schneebeli, S. T. (Contributor), Wasielewski, M. R. (Contributor), Stoddart, J. F. (Contributor) & Langen, P. L. (Contributor), Cambridge Crystallographic Data Centre, 2014
DOI: 10.5517/cc12cgnk, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc12cgnk&sid=DataCite
Dataset
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CCDC 994126: Experimental Crystal Structure Determination
Wu, Y. (Creator), Frasconi, M. (Creator), Gardner, D. M. (Creator), McGonigal, P. R. (Creator), Schneebeli, S. T. (Creator), Wasielewski, M. R. (Creator) & Stoddart, J. F. (Creator), Cambridge Crystallographic Data Centre, 2014
DOI: 10.5517/cc12cglh, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc12cglh&sid=DataCite
Dataset
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CCDC 994127: Experimental Crystal Structure Determination
Wu, Y. (Creator), Frasconi, M. (Creator), Gardner, D. M. (Creator), McGonigal, P. R. (Creator), Schneebeli, S. T. (Creator), Wasielewski, M. R. (Creator) & Stoddart, J. F. (Creator), Cambridge Crystallographic Data Centre, 2014
DOI: 10.5517/cc12cgmj, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc12cgmj&sid=DataCite
Dataset