Novel supramolecular compounds based on tetrathiafulvalene tetracarboxylate with the cationic chains and anionic chains: Syntheses, charactarization and magnetic propertises

Seven supramolecular framework, [M(bipy)2(H2O)4][M(TC–TTF)(H2O)2] (M=Mn 1, Co 2, Fe 3, Cu 4, Zn 5 and Cd 6; H4TC–TTF=tetrathiafulvalene tetracarboxylate; bipy=4,4′-bipyridine) and [Fe4(μ2-Cl)6(OH2)12][H2.5(TC–TTF)]4·4H2O 7 have been prepared by using a diffusion method. 1–6 are isomorphous and crystallize in monoclinic crystal system, space group P21/c (1–5), and C2/m (6), respectively. {[M(TC–TTF)(H2O)2]2−}n is a 1D polymer anionic chain consisting of MII bridged by TC–TTF4−. {[M(bipy)2(H2O)4]2+}n cation forms 1D cationic chain by π···π stacks, and then are linked through O–H···O (N) hydrogen-bonding and π···π interactions to construct a 2D supramolecular net. Furthermore, the 2D nets are connected through O–H···O hydrogen-bonding interactions and form a 3D supramolecular framework. 7 displays a 3D supramolecular framework by O–H···O hydrogen-bonding and S···S interactions with a 1D open channel. Variable–temperature magnetic susceptibility measurements for 1 and 2 show antiferromagnetic coupling interactions at 1.8–300K.