Inorganic macrocycles, based on non‐carbon backbones, present exciting synthetic
challenges in the systematic assembly of inorganic molecules, as well as new avenues in
host–guest and supramolecular chemistry. Here we demonstrate a new high‐yielding
modular approach to a broad range of trimeric and hexameric S‐and Se‐bridged inorganic
macrocycles based on cyclophosphazane frameworks, using the building blocks [S=(H) P (μ‐
NR)] 2. The method involves the in situ generation of the key intermediate [E (S) P (μ‐NR)] …

Inorganic macrocycles, based on non‐carbon backbones, present exciting synthetic
challenges in the systematic assembly of inorganic molecules, as well as new avenues in
host–guest and supramolecular chemistry. Here we demonstrate a new high‐yielding
modular approach to a broad range of trimeric and hexameric S‐and Se‐bridged inorganic
macrocycles based on cyclophosphazane frameworks, using the building blocks [S=(H) P (μ‐
NR)] 2. The method involves the in situ generation of the key intermediate [Eurn: x-wiley …