Solid-Gas Phase Synthesis of Coordination Networks by Using Redox-Active Ligands and Elucidation of Their Oxidation Reaction.

Formation of coordination networks is a complex process affected by a multitude of factors. Many synthetic strategies have been developed that attempt to control these factors and direct the structure of the final product. Coordination bond formation and structural assembly processes, however, typically take place either in the solution or solid states. In comparison, gas-phase network synthesis remains largely unexplored. Herein, two new two-dimensional coordination networks are obtained from the solid-gas phase reaction between ZnX2 (X=I, Br) and the redox-active 2,5,8-tri(4-pyridyl)1,3-diazaphenalene (HTPDAP) ligand. Their structures were solved by ab initio powder X-ray diffraction analysis and feature a novel Zn halide trimeric cluster. This strategy is contrasted with a conventional solvothermal synthesis, which led to a one-dimensional coordination polymer instead. The intrinsic electroactive properties of these materials were probed by solid-state cyclic voltammetry measurements, which revealed the presence of HTPDAP and halide-based processes. Chemical oxidation of the two-dimensional networks by using NOPF6 agent, unexpectedly, led to the formation of a nitrated analog of HTPDAP, the PF6 - salt of diprotonated 4,6,7,9-tetranitro-2,5,8-tris(4-pyridyl)diazaphenalene cation (denoted N-TPDAP), which was isolated and characterized. These results provide deeper insights into the oxidation process of HTPDAP-containing networks and uncover unique redox-induced chemical transformations.

Control of anisotropy of a redox-active molecule-based film leads to non-volatile resistive switching memory.

Control of the π-π interaction direction in a redox-active π-molecule based film led to the formation of new mechanistic nonvolatile resistive switching memory: a redox-active organic molecule, 2,5,8-tri(4-pyridyl)1,3-diazaphenalene, showed non-volatile bistable resistance states with a high on-off ratio, retention, and endurance only when the molecular orientation was anisotropic. Control experiments using redox-active/redox-inert organic molecules with isotropic/anisotropic molecular orientations implied that the formation of conductive oxidized π-π stacking layers from non-conductive neutral π-π stacking layers is responsible for resistive switching phenomena, indicating new mechanisms such as ReRAM. Our findings will give a comprehensive understanding of electron transport in organic solid materials based on the effects of redox-activity and molecular arrangement, leading to fabrication of a new class of ReRAM based on organic molecules.