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Pyrrole Annulation Controls Protonation-Induced Topology Switching in π-Extended Core-Modified Figure-of-Eight
Sumit Sahoo1, Sergio Moles Quintero2, Mercedes Alonso2
1School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A/2B Raja S.C Mullick Road, Jadavpur, Kolkata, West Bengal 700 032, India.
Abstract:
Two π-extended core-modified figure-of-eight [38]hexaphyrins(6.1.1.6.1.1) exhibiting strong NIR absorption were synthesized to examine how pyrrole annulation controls protonation-induced topology switching and aromaticity modulation. The nonannulated system undergoes protonation-driven planarization with enhanced global aromaticity, whereas β-annulation rigidifies the macrocycle and preserves the figure-of-eight topology upon protonation. TD-DFT calculations, aromaticity descriptors, and ring-current analysis show that annulation localizes the electronic response and that the NIR Q-type bands arise mainly from local excitations rather than global aromaticity.
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