Synergic Topological- and Size-Control on Phosphazane Chemistry: First Unfolded Hybrid Tetrameric Macrocycle

Herein, we report an unprecedented combination of pre-arranged building blocks and a multi-step synthetic route to rationally and simultaneously enable access to an unfolded tetrameric macrocycle, which is not accessible using conventional synthetic strategies. The obtained macrocycle, cis-[μ-P(μ-NtBu)]2(μ-p-OC6H4C(O)O)]4[μ-P(μ-NtBu)]2 (4), is the first unfolded open-face hybrid cyclodiphosphazane macrocycle reported and displays a cavity area of 110.1 Å2 - the largest of its kind.