84.
Novel diacetylene macrocycles
1 and
2 bearing dibenzylphosphine oxide were synthesised via Eglinton acetylenic intramolecular coupling. The X-ray analysis of crystals of macrocycles
1 and
2 demonstrated that the better-aligned tubular supramolecular structure was formed in macrocycle
1 than in macrocycle
2, which provided the possibility of diacetylene topochemical polymerisation in solid state of macrocycle
1. UV–vis, Raman spectroscopy and X-ray analysis indicated that the crystals of macrocycle 1 could undergo topochemical diacetylene polymerisation only on their surface by light irradiation; differential scanning calorimetry, solid-state
13C NMR spectroscopy and solubility test demonstrated that the crystals of macrocycle
1 could undergo diacetylene topochemical polymerisation inside solid by heat. As expected, based on the topological analysis of crystal structure, the crystals of macrocycle
2 could not undergo diacetylene topochemical polymerisation either by light irradiation or heat.
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