End-to-end communication in a linear supermolecule with a BOPHY centre and N,N-dimethylanilino-based terminals

Woodford, Owen J.; Stachelek, Patrycja; Ziessel, Raymond; Algoazy, Nawaf; Knight, Julian G.; Harriman, Anthony

Abstract

The recently introduced BOPHY (i.e., symmetrical bis(pyrrole-BF2)) chromophore is a highly attractive building block for constructing linear molecules with extended π-conjugation running along the molecular backbone. In order to assess the level of electronic communication between the terminal groups in this type of supermolecule, we have examined selective protonation and oxidation of the bis-(N,N-dimethylanilino-styryl) derivative. The amino N atoms are separated by 22.6 Å via a conjugated pathway but there is no indication of through-bond electronic coupling. Instead, the disparate pKa values and also reduction potentials found for one-electron oxidation of each aniline group are well explained in terms of very long-range electrostatic interactions. It is necessary, however, to allow for the effects of ion-pairing. As an interesting aside, it is shown that protonation can be achieved in a cast PMMA film by using a suitable photo-acid generator.

Citation

Woodford, O. J., Stachelek, P., Ziessel, R., Algoazy, N., Knight, J. G., & Harriman, A. (2018). End-to-end communication in a linear supermolecule with a BOPHY centre and N,N-dimethylanilino-based terminals. New Journal of Chemistry, 42(7), https://doi.org/10.1039/c7nj04654e

• Journal Article Type: Article
• Acceptance Date: Feb 12, 2018
• Online Publication Date: Feb 13, 2018
• Publication Date: Apr 7, 2018
• Deposit Date: Dec 7, 2020
• Journal: New Journal of Chemistry
• Print ISSN: 1144-0546
• Electronic ISSN: 1369-9261
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 42
• Issue: 7
• DOI: https://doi.org/10.1039/c7nj04654e
• Public URL: https://durham-repository.worktribe.com/output/1249718