Spectroscopic, Morphological, and Mechanistic Investigation of the Solvent‐Promoted Aggregation of Porphyrins Modified in meso‐Positions by Glucosylated Steroids

Abstract

Solvent‐driven aggregation of a series of porphyrin derivatives was studied by UV/Vis and circular dichroism spectroscopy. The porphyrins are characterised by the presence in the meso positions of steroidal moieties further conjugated with glucosyl groups. The presence of these groups makes the investigated macrocycles amphiphilic and soluble in aqueous solvent, namely, dimethyl acetamide/water. Aggregation of the macrocycles is triggered by a change in bulk solvent composition leading to formation of large architectures that express supramolecular chirality, steered by the presence of the stereogenic centres on the periphery of the macrocycles. The aggregation behaviour and chiroptical features of the aggregates are strongly dependent on the number of moieties decorating the periphery of the porphyrin framework. In particular, experimental evidence indicates that the structure of the steroid linker dictates the overall chirality of the supramolecular architectures. Moreover, the porphyrin concentration strongly affects the aggregation mechanism and the CD intensities of the spectra. Notably, AFM investigations reveal strong differences in aggregate morphology that are dependent on the nature of the appended functional groups, and closely in line with the changes in aggregation mechanism. The suprastructures formed at lower concentration show a network of long fibrous structures spanning over tens of micrometres, whereas the aggregates formed at higher concentration have smaller rod‐shaped structures that can be recognised as the result of coalescence of smaller globular structures. The fully steroid substituted derivative forms globular structures over the whole concentration range explored. Finally, a rationale for the aggregation phenomena was given by semiempirical calculations at the PM6 level.

Supramolecular Chirality in Porphyrin Chemistry

“…Whilst the monomeric species was essentially CD silent, the corresponding self-coordinated complex exhibited a noticeable CD signal in the region of Soret absorption consisting of three Cotton effects as a result of the interporphyrin exciton coupling. A different type of supramolecular self-assembly was employed for the chiral porphyrins, 109, 110 ( Figure 30) [89]. Whilst the monomeric species showed a rather weak monosignate Cotton effect (less than 10 cm…”

Self‐Organization of Polar Porphyrinoids

“…Aggregation of porphyrin derivatives 7 a , b bearing steroidal moieties further conjugated with glucosyl groups in the meso position led to supramolecular chiral architectures in a dimethyl acetamide (DMAc)/water mixture 22. The overall chirality of the architectures is controlled by the structure of the steroidal moieties.…”

Tuning the morphology of mesoscopic structures of porphyrin macrocycles functionalized by an antimicrobial peptide

“…These results would be of great importance, among others, for the development of solid-state sensors featuring stereoselective properties, presently pursued in our group [25][26][27][28]. Magnification of the boxed area in Figure 6A, showing small clusters of globular structures.…”