First examples of metal-organic frameworks with the novel 3,3'-(1,2,4,5-tetrazine-3,6-diyl)dibenzoic spacer. Luminescence and adsorption properties.

We report the synthesis of a novel ligand, 3,3'-(1,2,4,5-tetrazine-3,6-diyl)dibenzoic acid (1). In this fragment, we have introduced two carboxylate groups with the aim of using this ligand as a linker to construct three-dimensional metal-organic frameworks (MOFs). We have been successful in the formation of zinc (2) and lanthanum (3) MOFs. The zinc compound is a two-dimensional structure, while the lanthanum material is a three-dimensional MOF with interesting channels. We include the luminescence and adsorption studies of these materials. Moreover, we have evaluated the in vitro toxicity of this novel ligand, concluding that it can be considered negligible.

Effect of the apical ligand on the geometry and magnetic properties of copper(ii)/mesoxalate trinuclear units.

Three new heterometallic metal-organic frameworks, namely, {(Ph4P)2[MnCu3(Hmesox)3Br(H2O)]·H2O}n (1), {(Ph4P)2[CoCu3(Hmesox)3Br]}n (2) and {(Ph4P)2[ZnCu3(Hmesox)3Br]·2.5H2O}n (3) were prepared and their structure and magnetic properties were investigated (H4mesox = mesoxalic acid, Ph4P+ = tetraphenylphosphonium). The structure of all the compounds consist of two interpenetrating opposite-chirality supramolecular cationic and polymeric anionic 3-D (10,3)-a networks, which results in chiral compounds. The anionic network is formed from the polymerization of [Cu3(Hmesox)3Br]4- units, working as three connectors, and M(ii) cations, working as three-connecting nodes, M = Mn(ii), Co(ii) and Zn(ii). The Ph4P+ cations build the cationic chiral supramolecular network opposite to the anionic one. Compounds 1 and 2 exhibit long-range magnetic ordering with critical temperatures of 7.2 K and 6.9 K, respectively. However, compound 3 does not display long-range order, but shows ferromagnetic and antiferromagnetic coupling among the Cu(ii) ions. The magnetic interactions are studied by DFT calculations and compared with related Cu(ii)-mesoxalate compounds previously reported.