Solvent-Driven Conformational Exchange for Amide-Linked Bichromophoric BODIPY Derivatives

Thakare, Shrikant; Stachelek, Patrycja; Mula, Soumyaditya; More, Ankush B.; Chattopadhyay, Subrata; Ray, Alok K.; Sekar, Nagaiyan; Ziessel, Raymond; Harriman, Anthony

Abstract

The fluorescence lifetime and quantum yield are seen to depend in an unexpected manner on the nature of the solvent for a pair of tripartite molecules composed of two identical boron dipyrromethene (BODIPY) residues attached to a 1,10-phenanthroline core. A key feature of these molecular architectures concerns the presence of an amide linkage that connects the BODIPY dye to the heterocyclic platform. The secondary amide derivative is more sensitive to environmental change than is the corresponding tertiary amide. In general, increasing solvent polarity, as measured by the static dielectric constant, above a critical threshold tends to reduce fluorescence but certain hydrogen bond accepting solvents exhibit anomolous behaviour. Fluorescence quenching is believed to arise from light-induced charge transfer between the two BODIPY dyes, but thermodynamic arguments alone do not explain the experimental findings. Molecular modelling is used to argue that the conformation changes in strongly polar media in such a way as to facilitate improved rates of light-induced charge transfer. These solvent-induced changes, however, differ remarkably for the two types of amide.

Citation

Thakare, S., Stachelek, P., Mula, S., More, A. B., Chattopadhyay, S., Ray, A. K., …Harriman, A. (2016). Solvent-Driven Conformational Exchange for Amide-Linked Bichromophoric BODIPY Derivatives. Chemistry - A European Journal, 22(40), 14356-14366. https://doi.org/10.1002/chem.201602354

• Journal Article Type: Article
• Acceptance Date: Jun 16, 2016
• Online Publication Date: Aug 16, 2016
• Publication Date: Sep 26, 2016
• Deposit Date: Dec 7, 2020
• Journal: Chemistry - A European Journal
• Print ISSN: 0947-6539
• Publisher: Wiley
• Volume: 22
• Issue: 40
• Pages: 14356-14366
• DOI: https://doi.org/10.1002/chem.201602354
• Public URL: https://durham-repository.worktribe.com/output/1249748