Synthesis and structures of naphthalene-bridged figure-of-eight hexaphyrin(2.1.2.1.2.1) and its Cu(II) and Ni(II) complexes

New naphthalene-bridged hexaphyrin(2.1.2.1.2.1) (Naphex) and its copper and nickel complexes (NaphexNi and NaphexCu) were synthesized. Single-crystal X-ray analysis confirmed the rigid figure-of-eight topology of Naphex, featuring three naphthalene bridges. Structural and spectroscopic characterization (HR-MS, NMR, UV-Vis) revealed non-aromaticity in Naphex and its metal complexes. This work highlights the critical role of naphthalene bridges in stabilizing non-classical macrocyclic topologies and tailoring optoelectronic properties via metal coordination.