Inorganic macrocycles remain challenging synthetic targets due to the limited number of strategies reported for their syntheses. Among these species, large fully inorganic cyclodiphosphazane macrocycles have been experimentally and theoretically highlighted as promising candidates for supramolecular chemistry. In contrast, their hybrid organic–inorganic counterparts are lagging behind due to the lack of synthetic routes capable of controlling the size and topological arrangement (i.e., folded vs unfolded) of the target macrocycle, rendering the synthesis of differently sized macrocycles a tedious screening process. Herein, we report—as a proof-of-concept—the combination of pre-arranged building blocks and a two-step synthetic route to rationally enable access a large unfolded tetrameric macrocycle, which is not accessible via conventional synthetic strategies. The obtained macrocycle hybrid cyclodiphosphazane macrocycle, cis-[μ-P(μ-NtBu)]2(μ-p-OC6H4C(O)O)]4[μ-P(μ-NtBu)]2 (4), displays an unfolded open-face cavity area of 110.1 Å2. Preliminary theoretical host–guest studies with the dication [MeNC5H4]22+ suggest compound 4 as a viable candidate for the synthesis of hybrid proto-rotaxanes species based on phosphazane building blocks.

Artificial molecular machines have captured the full attention of the scientific community since Jean-Pierre Sauvage, Fraser Stoddart, and Ben Feringa were awarded the 2016 Nobel Prize in Chemistry. The past and current developments in molecular machinery (rotaxanes, rotors, and switches) primarily rely on organic-based compounds as molecular building blocks for their assembly and future development. In contrast, the main group chemical space has not been traditionally part of the molecular machine domain. The oxidation states and valency ranges within the p-block provide a tremendous wealth of structures with various chemical properties. Such chemical diversitywhen implemented in molecular machinescould become a transformative force in the field. Within this context, we have rationally designed a series of NH-bridged acyclic dimeric cyclodiphosphazane species, [(μ-NH){PE(μ-NtBu)2PE(NHtBu)}2] (E = O and S), bis-PV 2N2, displaying bimodal bifurcated R2 1(8) and trifurcated R3 1(8,8) hydrogen bonding motifs. The reported species reversibly switch their topological arrangement in the presence and absence of anions. Our results underscore these species as versatile building blocks for molecular machines and switches, as well as supramolecular chemistry and crystal engineering based on cyclophosphazane frameworks.

Molecular machines and switches, supramolecular chemistry, and crystal engineering are vibrant areas of research. Organic chemists have devoted considerable efforts to develop a wide range of complex functional building blocks with enhanced properties and chemically responsive properties to advance these fields. However, the rational design of topologically versatile and chemically responsive building blocks in the main group arena is largely unexplored. Within this context, we have rationally designed a series of NH-bridged acyclic dimeric cyclodiphosphazanes species, [(μ-NH){PE(μ-NtBu)2PE(NHtBu)}2] (E= O and S), displaying bimodal bifurcated R21(8) and trifurcated R31(8,8) hydrogen bonding motifs. The reported species reversibly switch their topological arrangement in the presence of anions. Our results underscore these species as versatile building blocks for molecular machines and switches, as well as supramolecular chemistry and crystal engineering based on cyclophosphazane frameworks.