Hydrogen-bonded supramolecular metal-imidazolate frameworks: gas sorption, magnetic and UV/Vis spectroscopic properties

By varying reaction parameters for the syntheses of the hydrogen-bonded metal-imidazolate frameworks (HIF) HIF-1 and HIF-2 (featuring 14 Zn and 14 Co atoms, respectively) to increase their yields and crystallinity, we found that HIF-1 is generated in two different frameworks, named as HIF-1a and HIF-1b. HIF-1b is isostructural to HIF-2. We determined the gas sorption and magnetic properties of HIF-2. In comparison to HIF-1a (Brunauer–Emmett–Teller (BET) surface area of 471 m 2 g −1 ), HIF-2 possesses overall very low gas sorption uptake capacities [BET(CO 2 ) surface area = 85 m 2 g −1 ]. Variable temperature magnetic susceptibility measurement of HIF-2 showed antiferromagnetic exchange interactions between the cobalt(II) high-spin centres at lower temperature. Theoretical analysis by density functional theory confirmed this finding. The UV/Vis-reflection spectra of HIF-1 (mixture of HIF-1a and b), HIF-2 and HIF-3 (with 14 Cd atoms) were measured and showed a characteristic absorption band centered at 340 nm, which was indicative for differences in the imidazolate framework.