Influence of the solvent in the self-assembly and binding properties of [1 + 1] tetra-imine bis-calix[4]pyrrole cages

• Published in: Chemical science (Cambridge) 2022-12, Vol.14 (1), p.186-195
• Main Authors: Mirabella, Chiara F. M, Aragay, Gemma, Ballester, Pablo
• Format: Article
• Language: English
• Subjects: Binding sites; Cages; Chemistry; Hydrogen bonding; Inclusion complexes; Mixtures; NMR spectroscopy; Pyridines; Self-assembly; Solvents; Stoichiometry
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d2sc05311j

We report the self-assembly of shape-persistent [1 + 1] tetra-imine cages 1 based on two different tetra-α aryl-extended calix[4]pyrrole scaffolds in chlorinated solvents and in a 9 : 1 CDCl 3  : CD 3 CN solvent mixture. We show that the use of a bis- N -oxide 4 (4,4′-dipyridyl- N,N ′-dioxide) as template is not mandatory to induce the emergence of the cages but has a positive effect on the reaction yield. We use 1 H NMR spectroscopy to investigate and characterize the binding properties (kinetic and thermodynamic) of the self-assembled tetra-imine cages 1 with pyridine N -oxide derivatives. The cages form kinetically and thermodynamically stable inclusion complexes with the N -oxides. For the bis- N -oxide 4 , we observe the exclusive formation of 1 : 1 complexes independently of the solvent used. In contrast, the pyridine- N -oxide 5 (mono-topic guest) produces inclusion complexes displaying solvent dependent stoichiometry. The bis- N -oxide 4 is too short to bridge the gap between the two endohedral polar binding sites of 1 by establishing eight ideal hydrogen bonding interactions. Nevertheless, the bimolecular 4 ⊂ 1 complex results as energetically favored compared to the 5 2 ⊂ 1 ternary counterpart. The inclusion of the N -oxides, 4 and 5 , in the tetra-imine cages 1 is significantly faster in chlorinated solvents (minutes) than in the 9 : 1 CDCl 3  : CD 3 CN solvent mixture (hours). We provide an explanation for the similar energy barriers calculated for the formation of the 4 ⊂ 1 complex using the two different ternary counterparts 5 2 ⊂ 1 and (CD 3 CN) 2 ⊂ 1 as precursors. We propose a mechanism for the in-out guest exchange processes experienced by the tetra-imine cages 1 . We report the self-assembly and binding properties of [1+1] tetra-imine cages based on two different tetra-α aryl-extended calix[4]pyrrole scaffolds in chlorinated solvents and in a 9 : 1 CDCl 3  : CD 3 CN solvent mixture.