Formation of a Macrocycles‐in‐a‐Macrocycle Superstructure with All‐gauche Conformation by Reversible Radical Association

Abstract

The formation of an unprecedented macrocycles-ina-macrocycle (MIM) superstructure by reversible radicalradical association of at riphenylamine based monomer terminated with three dicyanomethyl radicals is presented. The reaction yield is nearly quantitative and the obtained macrocycle contains three small dimeric macrocycles according to X-rayc rystallographic analysis.T he six monomer molecules are linked by nine long dynamic covalent C(sp 3 ) À C(sp 3 )b onds that all adopt ag auche conformation. Such aconformation favors the formation of aMIM structure rather than a2 Dn etwork with an all-anti conformation. Tw o enantiomers with left-/ right-handed chirality exist in the single crystals of the superstructure.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Lewis Acid‐Mediated Radical Stabilization and Dynamic Covalent Bonding: Tunable, Reversible and Photocontrollable

“…Herein we report that the stabilization of a radical as well as its dynamic covalent bonding can be efficiently controlled by the coordination of a Lewis acid. We choose Lewis acid B(C 6 F 5 ) 3 (BCF) and the σ‐dimer of phenylamine substituted dicyanomethyl radical for study on the basis of considering: (a) Equilibria between dicyanomethyl radicals and their σ‐dimers recently have been an excellent model of DCC (Scheme 1b) [5, 8–31] . The stability of dicyanomethyl radicals has been systematically studied by structural modification; (b) BCF is an oxidizing agent and can oxidize an organic molecule to a radical cation by single electron transfer [33, 34] .…”

Dynamic Covalent Properties of a Novel Indolo[3,2‐b]carbazole Diradical

“…[5][6][7] Reversible homolytic covalent bond cleavage/formation involving radicals peciesh as been recently demonstrated to be an efficient strategy to obtain multi-responsivec hromic soft materials. [5][6][7][8][9][10][11][12][13][14][15] Owing to this property,o rganic mono-and diradicals have emerged as essential building blocks in dynamic covalent chemistry (DCC). [16][17][18] Theu nique feature of the open-shell systems to form weak self-assembled molecular complexes has earmarked organic radicals as prospective for ag reat number of applications such as stimuli-responsives oft materials, [5][6][7] spintronics, [19] spin-crossover materials [20,21] or molecular self-assembly.…”