Redox-Programmable Spin-Crossover Behaviors in a Cationic Framework

Metal-organic frameworks (MOFs) provide versatile platforms to construct multi-responsive materials. Herein, by introducing the neutral tetradentate ligand and the linear dicyanoaurate(I) anion, we reported a rare cationic MOF [Fe^II(TPB){Au^I(CN)₂}]I·4H₂O·4DMF (TPB = 1,2,4,5-tetra(pyridin-4-yl)benzene) with hysteretic spin-crossover (SCO) behavior near room temperature. This hybrid framework with an open metal site (Au^I) exhibits redox-programmable capability toward dihalogen molecules. By means of post-synthetic modification, all the linear [Au^I(CN)₂]^- linkers can be oxidized to square planar [Au^III(CN)₂X₂]^- units, which results in the hysteretic SCO behaviors switching from one-step to two-step for Br₂ and three-step for I₂. More importantly, the stepwise SCO behaviors can go back to one-step via the reduction by l-ascorbic acid (AA). Periodic DFT calculations using various SCAN-type exchange-correlation functionals have been employed to rationalize the experimental data. Hence, these results demonstrate for the first time that switchable one-/two-/three-stepped SCO dynamics can be manipulated by chemical redox reactions, which opens a new perspective for multi-responsive molecular switches.