Mechanical insulation of aza-Pechmann dyes within [2]rotaxanes.

Autor:	Cutillas-Font G; Department of Organic Chemistry, Faculty of Chemistry, University of Murcia, Regional Campus of International Excellence Campus Mare Nostrum 30100 Murcia Spain aureliap@um.es ppberna@um.es., Pastor A; Department of Organic Chemistry, Faculty of Chemistry, University of Murcia, Regional Campus of International Excellence Campus Mare Nostrum 30100 Murcia Spain aureliap@um.es ppberna@um.es., Alajarin M; Department of Organic Chemistry, Faculty of Chemistry, University of Murcia, Regional Campus of International Excellence Campus Mare Nostrum 30100 Murcia Spain aureliap@um.es ppberna@um.es., Martinez-Cuezva A; Department of Organic Chemistry, Faculty of Chemistry, University of Murcia, Regional Campus of International Excellence Campus Mare Nostrum 30100 Murcia Spain aureliap@um.es ppberna@um.es., Marin-Luna M; Department of Organic Chemistry, Faculty of Chemistry, University of Murcia, Regional Campus of International Excellence Campus Mare Nostrum 30100 Murcia Spain aureliap@um.es ppberna@um.es., Batanero B; Department of Organic Chemistry and Inorganic Chemistry, University of Alcala, Institute of Chemical Research AndrésM. del Rio 28805 Alcalá de Henares Madrid Spain., Berna J; Department of Organic Chemistry, Faculty of Chemistry, University of Murcia, Regional Campus of International Excellence Campus Mare Nostrum 30100 Murcia Spain aureliap@um.es ppberna@um.es.
Jazyk:	angličtina
Zdroj:	Chemical science [Chem Sci] 2024 Jul 31; Vol. 15 (34), pp. 13823-13831. Date of Electronic Publication: 2024 Jul 31 (Print Publication: 2024).
DOI:	10.1039/d4sc03657c
Abstrakt:	Aza-Pechmann derivatives have emerged as interesting building blocks for the preparation of organic electronic devices. The development of methodologies aimed to enhance their chemical stability and modulate their physical and chemical properties constitutes an interesting goal. Here we report the synthesis of mechanically interlocked aza-Pechmann dyes with benzylic amide macrocycles, along with the study of how the mechanical bond impacts their stability, photophysical and redox properties. Rotaxanes composed of Pechmann dilactams as threads exhibit one of the highest energy barriers for macrocyclic ring rotation, highlighting the strength of the attractive interactions ring-thread within the interlocked structure. Their enhanced thermal stability, compared to the non-interlocked counterparts, evidences the protective role of the macrocycle. Computational and electrochemical analyses indicate that the benzylic amide macrocycle improves the stability of the HOMO and LUMO orbitals of the interlocked dyes. Finally, spectroscopic and electrochemical data reveal that the macrocycle subtly modulates the optoelectronic and redox behaviour of the Pechmann dilactams. Competing Interests: There are no conflicts to declare. (This journal is © The Royal Society of Chemistry.)
Databáze:	MEDLINE
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