Reversible Photocapture Of A [2]Rotaxane Harnessing A Barbiturate Template

Photoirradiation of a hydrogen-bonded molecular complex comprising acyclic components, namely, a stoppered thread (1) with a central barbiturate motif and an optimized doubly anthracene-terminated acyclic Hamilton-like receptor (2b), leads to an interlocked architecture, which was isolated and fully characterized. The sole isolated interlocked photoproduct (Phi = 0.06) is a [2]rotaxane, with the dimerized anthracenes assuming a head-to-tail geometry, as evidenced by NMR spectroscopy and consistent with molecular modeling (PM6). A different behavior was observed on irradiating homologous molecular complexes 1 subset of 2a, 1?2b, and 1 subset of 2c, where the spacers of 2a, 2b, and 2c incorporated 3, 6, and 9 methylene units, respectively. While no evidence of interlocked structure formation was observed following irradiation of 1 subset of 2a, a kinetically labile rotaxane was obtained on irradiating the complex 1 subset of 2c, and ring slippage was revealed. A more stable [2]rotaxane was formed on irradiating 1 subset of 2b, whose capture is found to be fully reversible upon heating, thereby resetting the system, with some fatigue (38%) after four irradiation-thermal reversion cycles.