New photoswitchable pyridyl-azo-phenyl-decorated tripodal host ligands (Laz) that belong to the cyclotriveratrylene family have been synthesized, and their photoswitching behavior and crystal structures determined. The latter includes a remarkable 7-fold Borromean-weave entanglement of π–π stacked layers. Trigonal bipyramidal {[Pd­(en)]3(Laz)2}6+ metallo-cryptophanes (en = ethylenediamine) were formed from these and a previously known pyridyl-azo-phenyl-decorated tripodal host ligand. These coordination cages dissociate at low concentrations and are less robust to photoswitching of the Laz ligands than were previously reported Ir­(III)-linked metallo-cryptophanes with similar ligands, reflecting the greater lability of the Pd–N bonds. The {[Pd­(en)]3(Laz)2}6+ cages all act as hosts, binding octyl sulfate anions, or N-[2-(dimethylamino)­ethyl]-1,8-naphthalimide in a dimethyl sulfoxide solution.

Trimetallic Pd–NHCs with a cyclotriguaiacylene scaffold display variable host–guest interactions and, along with monomeric analogues, catalyse cross-coupling reactions with a switch in the normal regioselectivity.