Compositional inhomogeneity and tuneable thermal expansion in mixed-metal ZIF-8 analoguesElectronic supplementary information (ESI) available. See DOI: 10.1039/c8cc04172e

We study the structural and thermomechanical effects of cation substitution in the compositional family of metal-organic frameworks Zn 1− x Cd x (mIm) 2 (HmIm = 2-methylimidazole). We find complete miscibility for all compositions x , with evidence of inhomogeneous distributions of Cd and Zn that in turn affect framework aperture characteristics. Using variable-temperature X-ray powder diffraction measurements, we show that Cd substitution drives a threefold reduction in the magnitude of thermal expansion behaviour. We interpret this effect in terms of an increased density of negative thermal expansion modes in the more flexible Cd-rich frameworks. We study the structural and thermomechanical effects of cation substitution in the compositional family of metal-organic frameworks Zn 1− x Cd x (mIm) 2 (HmIm = 2-methylimidazole).