Delocalized TCNQ Stacks in Nickel and Copper Tetraazamacrocyclic Systems

New derivatives of formula [M(dieneN4)](TCNQ)3, M = Ni or Cu and dieneN4 = cis- or trans-hexamethyltetraazacyclotetradecadiene, have been obtained. The TCNQ units show electronic delocalization and formation of
1D stacks, with no direct interactions with the metal cations. The stack is not uniform and can be seen as formed
by trimeric dianions (TCNQ)32-. The electronic delocalization favors the conductivity in these materials, which
behave as good semiconductors. The crystal structures of the trans derivatives have been solved:  [Ni(trans-dieneN4)](TCNQ)3, triclinic, P-1, a = 8.809(2) Å, b = 10.896(2) Å, c = 13.727(2) Å, α = 103.04(1)°, β =
101.23(2)°, γ = 109.37(2)°, Z = 1; [Cu(trans-dieneN4)](TCNQ)3:  triclinic, P-1, a = 7.872(1) Å, b = 9.840(1)
Å, c = 14.819(1) Å, α = 92.32(1)°, β = 95.05(1)°, γ = 95.66(1)°, Z = 1.