Structural Phase Transformations Induced by Guest Molecules in a Nickel-Based 2D Square Lattice Coordination Network

Herein, we report the crystal structure and guest binding properties of a new two-dimensional (2D) square lattice (sql) topology coordination network, sql-(azpy)­(pdia)-Ni, which is comprised of two linker ligands with diazene (azo) moieties, (E)-1,2-di­(pyridin-4-yl)­diazene­(azpy) and (E)-5-(phenyldiazenyl)­isophthallate­(pdia). sql-(azpy)­(pdia)-Ni underwent guest-induced switching between a closed (nonporous) β phase and several open (porous) α phases, but unlike the clay-like layer expansion to distinct phases previously reported in switching sql networks, a continuum of phases was formed. In effect, sql-(azpy)­(pdia)-Ni exhibited elastic-like properties induced by adaptive guest binding. Single-crystal X-ray diffraction (SCXRD) studies of the α phases revealed that the structural transformations were enabled by the pendant phenyldiazenyl moiety on the pdia2– ligand. This moiety functioned as a type of hinge to enable parallel slippage of layers and interlayer expansion for the following guests: N,N-dimethylformamide, water, dichloromethane, para-xylene, and ethylbenzene. The slippage angle (interplanar distances) ranged from 54.133° (4.442 Å) in the β phase to 69.497° (5.492 Å) in the ethylbenzene-included phase. Insight into the accompanying phase transformations was also gained from variable temperature powder XRD studies. Dynamic water vapor sorption studies revealed a stepped isotherm with little hysteresis that was reversible for at least 100 cycles. The isotherm step occurred at ca. 50% relative humidity (RH), the optimal RH value for humidity control.