Chemical/Physical Pressure Tunable Spin-Transition Temperature and Hysteresis in a Two-Step Spin Crossover Porous Coordination Framework

A two-dimensional (2D) square-grid type porous coordination polymer [Fe­(bdpt)2]·guest (1·g, Hbdpt = 3-(5-bromo-2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole) with isolated small cavities was designed and constructed as a spin-crossover (SCO) material based on octahedral FeIIN6 units and an all-nitrogen ligand. Three guest-inclusion forms were successfully prepared for 1·g (1·EtOH for g = ethanol, 1·MeOH for g = methanol, 1 for g = Null), in which the guest molecules interact with the framework as hydrogen-bonding donors. Magnetic susceptibility measurements showed that 1·g exhibited two-step SCO behavior with different transition temperatures (1·EtOH 1·MeOH 1) and hysteresis widths (1·EtOH > 1·MeOH > 1 ≈ 0). Such guest modulation of two-step spin crossover temperature and hysteresis without changing two-step state in a porous coordination framework is unprecedented. X-ray single-crystal structural analyses revealed that all two-step SCO processes were accompanied with interesting symmetry-breaking phase transitions from space group of P21/n for all high-spin Fe­(II), to P1̅ for ordered half high-spin and half low-spin Fe­(II), and back to P21/n for all low-spin Fe­(II) again by lowering temperature. The different SCO behaviors of 1·g were elucidated by the steric mechanism and guest–host hydrogen-bonding interactions. The SCO behavior of 1·g can be also controlled by external physical pressure.