The reaction of AsCl3 with H2L (where L= a rigid dithiolate) results in the self-assembly of As2L2Cl2 supramolecular macrocycles. For ligands 4, 4′-bis (mercaptomethyl) biphenyl (H21), 4, 4′-bis (mercaptomethyl)-trans-stilbene (H22), and 1, 4-dimethoxy-2, 5-bis (mercaptomethyl) benzene (H23), the macrocyclic cavities of the resulting assemblies are large enough to host aromatic solvent molecules, as revealed by single crystal X-ray ...