New photoswitchable pyridyl-azo-phenyl-decorated tripodal host ligands (Laz) that belong to the cyclotriveratrylene family have been synthesized, and their photoswitching behavior 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 form...