Synthesis of Phosphorus-Centered and Chalcogen-Bridged Concave Molecules: Modulation of Bowl Geometries and Packing Structures by Changing Bridging Atoms

A series of phosphorus-centered concave molecules having oxygen and sulfur as bridging atoms, C3v-symmetric P4 and Cs-symmetric P2 and P3, were newly synthesized. The packing diagrams of the concave molecules P1–P4 are dependent on the bridging atoms, columnar structures for P1 and P4, and zigzag structures for P2 and P3. The bowl depth becomes shallower in the order of P1, P2, P3, and P4 as the number of bridging sulfur atoms increases.