Chiral diketopyrrolo[3,4-c]pyrrole dyes with different substitution symmetry: impact of adamantyl groups on the photo-physical properties in solution and thin films

Chiral diketopyrrolo[3,4-c]pyrrole dyes with different substitution symmetry: impact of adamantyl groups on the photo-physical properties in solution and thin films

Článek WoS

Here we propose a comparative study on four chiral 1,4-diketo-3,6-dithienylpyrrolo[3,4-c]pyrrole (DPP) dyes with different substitution symmetry on the lactam moieties: (i) symmetrically N-substituted dyes 1–2, bearing two (S)-β-citronellyl (DPP-CT) or (S)-2-methylbutyl (DPP-MT) chains; (ii) non-symmetrically N-substituted dyes 3–4, where an adamantylmethyl appendage replaced one of the (S)-β-citronellyl (DPP-ACT) or (S)-2-methylbutyl (DPP-AMT) chains. The four molecules were synthesized and subjected to detailed investigation of their photo-physical properties in solution (absorbance, fluorescence, cyclic voltammetry) and thin films (absorbance, electronic circular dichroism, optical microscopy), evaluating the impact of different chiral moieties (citronellyl vs. 2-methylbutyl chains) and of different substitution patterns exerted by the adamantane moiety (symmetrical vs. non-symmetrical DPPs). Special emphasis was given to the chiroptical study of thin films, discussing the origin of different supramolecular arrangements in the solid state. Putting together experimental and computational results, we rationalize the chiroptical behavior of these systems in comparison with that of other classes of DPP dyes recently investigated by our group.

Here we propose a comparative study on four chiral 1,4-diketo-3,6-dithienylpyrrolo[3,4-c]pyrrole (DPP) dyes with different substitution symmetry on the lactam moieties: (i) symmetrically N-substituted dyes 1–2, bearing two (S)-β-citronellyl (DPP-CT) or (S)-2-methylbutyl (DPP-MT) chains; (ii) non-symmetrically N-substituted dyes 3–4, where an adamantylmethyl appendage replaced one of the (S)-β-citronellyl (DPP-ACT) or (S)-2-methylbutyl (DPP-AMT) chains. The four molecules were synthesized and subjected to detailed investigation of their photo-physical properties in solution (absorbance, fluorescence, cyclic voltammetry) and thin films (absorbance, electronic circular dichroism, optical microscopy), evaluating the impact of different chiral moieties (citronellyl vs. 2-methylbutyl chains) and of different substitution patterns exerted by the adamantane moiety (symmetrical vs. non-symmetrical DPPs). Special emphasis was given to the chiroptical study of thin films, discussing the origin of different supramolecular arrangements in the solid state. Putting together experimental and computational results, we rationalize the chiroptical behavior of these systems in comparison with that of other classes of DPP dyes recently investigated by our group.

electronic circular dichroism, optical microscopy, Chiral diketopyrrolo[3,4-c]pyrrole dyes, adamantane moiety

electronic circular dichroism, optical microscopy, Chiral diketopyrrolo[3,4-c]pyrrole dyes, adamantane moiety

Martin Cigánek, Claudio Vatteroni, Francesca Romana Lauro, Francesco Zinna, Gennaro Pescitelli, Jozef Krajčovič, Gianluigi Albano

10.06.2025

ROYAL SOC CHEMISTRY

1477-0520

ORGANIC & BIOMOLECULAR CHEMISTRY

28

23

Spojené království Velké Británie a Severního Irska

6718

6737

19

https://pubs.rsc.org/en/content/articlelanding/2025/ob/d5ob00782h

http://hdl.handle.net/