Dynamic Interplay between Spin-Crossover and Host-Guest Function in a Nanoporous Metal-Organic Framework Material

摘要

The nanoporous metal-organic framework [Fe(pz)Ni(CN)_4], 1 (where pz is pyrazine), exhibits hysteretic spin-crossover at ambient conditions and is robust to the adsorption and desorption of a wide range of small molecular guests, both gases (N_2, O_2, CO_2) and vapors (methanol, ethanol, acetone, acetonitrile, and toluene). Through the comprehensive analysis of structure, host-guest properties, and spin-crossover behaviors, it is found that this pillared Hofmann system uniquely displays both guest-exchange-induced changes to spin-crossover and spin-crossover-induced changes to host-guest properties, with direct dynamic interplay between these two phenomena. Guest desorption and adsorption cause pronounced changes to the spin-crossover behavior according to a systematic trend in which larger guests stabilize the high-spin state and therefore depress the spin-crossover temperature of the host lattice. When stabilizing the alternate spin state of the host at any given temperature, these processes directly stimulate the spin-crossover process, providing a chemisensing function. Exploitation of the bistability of the host allows the modification of adsorption properties at a fixed temperature through control of the host spin state, with each state shown to display differing chemical affinities to guest sorption. Guest desorption then adsorption, and vice versa, can be used to switch between spin states in the bistable temperature region, adding a guest-dependent memory effect to this system.