Synthesis and Dimerization Studies of a Lipophilic Photoresponsive Aryl-Extended Tetraurea-Calix[4]pyrrole.

We describe the syntheses of the lipophilic aryl-extended α,α,α,α-tetraurea-phenyl-calix[4]pyrrole 1, featuring four appended azo-phenyl groups with two tert-butoxy carbonyl meta-substituents and its photo-inactive counterpart 2. In CD2 Cl2 solutions, both tetraurea-calix[4]pyrroles self-assemble into dimeric capsules by encapsulating one molecule of a suitable bis-N-oxide or two molecules of a mono-N-oxide. The dimeric capsules are mainly stabilized by a cyclic array of sixteen hydrogen bonds established between the eight unidirectionally oriented urea groups. Photoirradiation experiments demonstrated the trans-to-cis isomerization of the azo-phenyl groups and the formation of a plethora of stereo isomeric cis-azo-enriched capsular assemblies. The highly cis-azo enriched capsular assemblies seem to show a reduced stability and their involvement in equilibria with non-capsular counterparts that also bind the N-oxides. The thermally induced cis-to-trans interconversion processes demonstrated the reversibility of the photoisomerization and the photostability of most binding partners. An equimolar mixture of the two tetraureas produced two homodimeric capsules and the heterodimeric counterpart in a ratio close to statistical distribution.