Application of C–H Functionalization in the Construction of Pyrene-Azobenzene Dyads

This paper is dedicated to the late Prof. Ramesh Kapoor (former faculty, IISER Mohali and Panjab University).

Abstract

Herein we report synthesis of pyrene-azobenzene dyads using the Pd(II)-catalyzed directing-group-assisted arylation of the ortho C(sp²)–H bond of pyrenecarboxamides as a key transformation. Many examples of directly connected pyrene-azobenzene dyads (without any linker) and glycine-based azobenzene-pyrene dyads have been synthesized. Initial incorporation of an acetanilide unit in the pyrene skeleton through Pd(II)-catalyzed directing-group-assisted ortho C(sp²)–H arylation by using iodoacetanilide was followed by the transformation of the acetanilide into an azobenzene unit to give the pyrene-azobenzene dyad. UV-Vis spectroscopic studies were performed to get the absorption properties (λ_max (nm)) of all the compounds. Preliminary photoswitching studies in both forward and reverse directions and their related thermal reverse Z→E isomerization kinetics measurements were ascertained for representative compounds. Considering the importance of pyrene and azobenzene linked motifs as important chromophore-based photoswitchable molecules in chemical, materials, and supramolecular sciences research fields, this work enriches the library of pyrene-azobenzene dyads.

Key words

azobenzene - C–H functionalization - directing group - palladium - photoswitching - pyrene

Publication History

Received: 02 June 2024

Accepted after revision: 10 September 2024

Accepted Manuscript online:
10 September 2024

Article published online:
14 October 2024

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