RESUMEN
Organic ionic plastic crystals (OIPCs) are a ductile soft material where the composing ions are in isotropic free rotation, while their positions are aligned in order. The rotational motion in its plastic phase promotes ion conduction by decreasing the activation energy. Here, we report novel OIPCs comprised of tetracyanoborate ([TCB]-) and various organic cations. In particular, the OIPC composed of [TCB]- and spiro-(1,1')-bipyrrolidinium ([spiropyr]+) cations can transform into its plastic phase at ultralow temperature (Tp = -55 °C) while maintaining a high melting point (Tm = 242 °C). Replacement of the cation with either tetraalkylammonium or phosphonium and comparing their phase behavior, the high Tm was attributed to the relatively small interionic distance between [spiropyr]+ and [TCB]-. At the same time, the low Tp was realized by the restricted vibrational mode of the spirostructure, allowing the initiation of isotropic rotational motion with less thermal energy input.
RESUMEN
Metal-organic frameworks (MOFs) are potential candidates for the platform of the solid acid; however, no MOF has been reported that has both aqueous ammonium stability and a strong acid site. This manuscript reports a highly stable MOF with a cation exchange site synthesized by the reaction between zirconium and mellitic acid under a high concentration of ammonium cations (NH4+). Single-crystal XRD analysis of the MOF revealed the presence of four free carboxyl groups of the mellitic acid ligand, and the high first association constant (pKa1) of one of the carboxyl groups acts as a monovalent ion-exchanging site. NH4+ in the MOF can be reversibly exchanged with proton (H+), sodium (Na+), and potassium (K+) cations in an aqueous solution. Moreover, the uniform nanospace of the MOF provides the acid site for selective NH4+ recovery from the aqueous mixture of NH4+ and Na+, which could solve the global nitrogen cycle problem. The solid acid nature of the MOF also results in the proton conductivity reaching 1.34 × 10-3 S cm-1 at 55 °C by ion exchange from NH4+ to H+.