Cooperative nanoparticle H-type self-assembly of a bolaamphiphilic BODIPY derivative in aqueous medium

• Published in: Polymer (Guilford) 2017-10, Vol.128, p.317-324
• Main Authors: Rödle, Alexander, Lambov, Martin, Mück-Lichtenfeld, Christian, Stepanenko, Vladimir, Fernández, Gustavo
• Format: Article
• Language: English
• Subjects: Amphiphilic systems; Aqueous chemistry; Aqueous self-assembly; BODIPY dyes; Chemical bonds; Hydrogen bonding; Hydrogen bonds; Hydrophobicity; Nanoparticles; NMR; Non-covalent interactions; Nuclear magnetic resonance; Self-assembly; Supramolecular chemistry; Water chemistry
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/j.polymer.2016.12.050

We report the H-type self-aggregation of a new linear water-soluble BODIPY bolaamphiphile equipped with amide groups and oligoethylene glycol chains. Intermolecular π-π interactions, amide-based hydrogen bonds and hydrophobic interactions lead to a highly cooperative self-assembly process. Detailed spectroscopic studies suggest that strong hydrophobic interactions are the driving force for a rotational displacement of the dye molecules within the stack in order to shield the hydrophobic π-system from water molecules. The so formed highly-ordered micellar structures have been further characterized by NMR, AFM, TEM, DLS studies and theoretical calculations. A new amide-containing bolaamphiphilic BODIPY dye has been synthesized and fully characterized. The self-assembly studies in water reveal a highly cooperative self-aggregation mechanism and the formation of micelles, driven by π-π interactions, amide-based hydrogen bonds and the hydrophobic effect. A further agglomeration of individual micelles to spherical nanoparticles is induced by CH-O interactions between the ambient hydrophilic oligoethyleneglycol chains. [Display omitted] •A new bolaamphiphilic BODIPY derivative with amide groups and peripheral glycol chains is described.•The system self-assembles in water into nanoparticle assemblies in a cooperative fashion.•Spectroscopic and theoretical studies reveal a face-to-face H-type stacking of the BODIPY dyes with a twisted dye arrangement.