Organic-inorganic hybrid materials from divalent metal cations and expanded N,N′-donor linkers

Abstract

Abstract The rod-shaped linker (E,E)-N,N′-(3,3′-dimethyl-4,4′-biphenyldiyl)bis[1-(3-pyridinyl)methanimine] (L) is exploited for the first time in the synthesis of extended structures. Four new coordination polymers of composition {[ZnL(OAc)2]·EtOH}n (1), {[CdL(OAc)2]·MeOH}n (2), {[Cu2L(OAc)4]·CH2Cl2}n (3) and [MnL(N3)2]n (4) have been structurally characterized. The metal cations and the anionic ancillary ligands play pivotal roles for the topology of these compounds. In the crystalline reaction products of Zn(II), Cd(II) and Cu(II) acetate with the organic linker, the acetate anions connects two neighboring cations to dinuclear [M2(OAc)4] subunits. These secondary building units are further crosslinked by the N,N′-donor ligand, either perpendicular to the acetato bridges, leading to a ladder-like ribbon for 1 and 2, or in the direction of the metal···metal separation, resulting in a simple chain in the case of 3. Instead of dinuclear secondary building units, a different topology results from reaction of the N,N′ linker with Mn(ClO4)2 in the presence of azide anions: 1,3 bridging by the N3 − groups leads to infinite chains. These are crosslinked by L in perpendicular direction, and the layer structure 4 is obtained. Natural bond orbital (NBO) analyses revealed information on the basis of orbital interactions about the coordination environments of the metal ions. Thermogravimetric measurements indicate the highest thermal stability for 2. Strong antiferromagnetic coupling within the dinuclear subunits of 3 is observed as a consequence of superexchange via the acetato bridges.