Supramolecular Architecture and Magnetic Properties of Copper(II) and Nickel(II) Porphyrinogen-TCNQ Electron-Transfer Salts

The compounds [Cu(Tz)(MeOH)2](TCNQ)2 (1), [Ni(Tz)(MeOH)2](TCNQ)2 (2), [Cu(Tz)2](TCNQ)7 (3) and [Ni(Tz)2](TCNQ)7 (4) (Tz=2,7,12,17‐tetramethyl‐1,6,11,16‐tetraazaporphyrinogen) were obtained by metathesis reaction of [M(Tz)](ClO4)2 with LiTCNQ and Et3NH(TCNQ)2, respectively. They were characterized by a combination of spectroscopic and physical methods. Compound 1 crystallizes in the monoclinic space group P21/n with a=8.310(2), b=25.180(4), c=20.727(4) Å, β=93.58(2)°; Z=4. Compound 3 crystallizes in the triclinic space group P$\bar 1$ with a=11.244(1), b=16.700(1), c=17.321(1) Å, α=113.47(1), β=108.52(1), γ=96.12(1)°; Z=2. The asymmetric unit of the compound 1 is formed by cationic [Cu(Tz)(MeOH)2]2+ and by two crystallographically non equivalent TCNQ.− anions; these anions form dimeric units by overlap of the π clouds. The dimers form hydrogen bonds with the metallomacrocyclic cation through the methanol ligands. According to this structure the compound is paramagnetic and behaves as an insulator in the temperature range studied. The paramagnetism arises only from the metal‐complex moieties. Compound 3 shows an unprecedented structure due to the steric requirements of the macrocycle that favors the stacking of the TCNQ groups. The structure consists of infinite stacks of TCNQ units separated by the metal‐macrocyclic units; there are seven TCNQ molecules per formula unit, one of which is formally mono‐anionic, while the other six bear one half of an electron per molecule. The copper is six‐coordinate in a very distorted octahedral environment. The Tz ligand is located in the equatorial plane and the apical nitrogens of the nitrile groups of two TCNQ molecules complete the coordination around the copper. The compound is a semiconductor and its magnetic behavior can be explained by the sum of the Curie contribution of the metal complex and the contribution arising from the magnetic‐exchange interactions of the spins located on the TCNQ units. The latter is found to be typical of one‐dimensional antiferromagnetic distorted chains of S=1/2 spins and can be fitted according to a one‐dimensional Heisenberg antiferromagnetic model. The flexibility and steric requirements of the porphyrinogen ligand in the metallomacrocycles described here influence the interactions with the TCNQ acceptor molecules, which form unprecedented stacks (see picture) with electronic delocalization along them.