In studies aimed at generating new self-assembling macrocyclic complexes for conductivity and modified electrode studies we prepared new azotetraazaannulene macrocycles and their Ni complexes. The temperature-dependent behaviour of these compounds as studied by DSC showed that while some were sensitive to decomposition, others readily formed a stable glassy material of the kind that has been observed in mesogenic organic compounds with bulky side groups. We have also investigated the self-assembly of these molecules onto gold electrode surfaces. The Co macrocyclic complex adsorbs such that the metal centre is no longer accessible to O2.