A new dicopper(II) complex with 3.6,9.16.19,22-hexaaza-6.19-bis(2-hydroxyethyl)-tricyclo[22,2,2,2(11.14)]triaconta-1,11,13,24,27, 29-hexaene(L), was synthesized and characterized. The crystal structure of [Cu2L(N-3)(2)](ClO4)(2) (.) 2H(2)O has shown that both Cu2+ ions are in penta-coordination environment with distorted trigonal bipyramid consisting of three N atoms from diethylenetriamine moieties. one N atom from azide and one O atom from hydroxyethyl pendant, and the separation of Cu...Cu is 8.11 Angstrom. The two aromatic rings are close to each other, the shortest distance being 3.71 Angstrom for C11...C21, and the benzene ring planes from a dihedral angle of 70.9 degrees in molecule. ES-MS spectra showed that the main species, [CU2(L-H)N-3](2+) and [Cu-2(L-2H)](2+), were formed by deprotonation of the hydroxyethyl pendants and releasing azides from the Cu(II) complex stepwise. (C) 2001 Elsevier Science B.V. All rights reserved.