Noble and transition metal aromatic frameworks: Synthesis, properties, and stability

In the first section, the electrical conductivity of rhodium phenylene-diisocyanide polymer is reported to be 3.4 x 10-11 S·cm-1. However, the conductivity also exhibits an inverse exponential decay in air with tau = 8 days. This change is attributed to the oxidation of the isocyanide functional group to an isocyanate, leading to a degradation in the long-range metal-metal bonding, the dominant conductivity mechanism. Using a more stable carboxylate ligand, the Cu terephthalate (TPA) system is studied and compared against the Mg, Co, Ni, and Zn terephthalates. A synthesis in N,N-dimethylformamide (DMF) is developed and large quantities of the Cu(TPA)·DMF can be synthesized in air. The crystal structure of the Cu(TPA)·DMF is shown to be in the C 2/m spacegroup. Upon desolvation, the Cu(TPA) is shown to have a large surface area of 625 m2g-1. The magnetic susceptibility of the Cu(TPA) indicates anti-ferromagnetic coupling between adjacent Cu centers in the same dimer. The thermal stability of the Zn, Ni, Co, and Mg terephthalates is shown to increase with decreasing symmetric carboxylate stretch in the IR. The magnetic susceptibilities of the Co and Ni terephthalates have paramagnetic behavior, with a Weiss temperature of theta = -12.9 K and theta = 8.8 for Co(TPA)·DMF and Ni(TPA)·DMF respectively. A heterometallic Zn-Cu terephthalate is synthesized with Cu concentrations ranging from 0 to 100%. Upon the addition of Cu, Zn-rich frameworks increase in surface area, change in thermal stability, and increase solvent retention from 16% to 25%. Zn is shown to couple with Cu in the same dimer at a high rate, changing the behavior of the dimer from anti-ferromagnetic to paramagnetic. The Weiss temperature suggests weak ferromagnetic interaction.