Highly Porous Cyanometallic Spin-Crossover Frameworks Employing Pyridazino[4,5-d]pyridazine Bridge

Abstract

Single crystals of two spin-crossover (SCO) cyanometallic coordination polymers based on the pyridazino[4,5-d]pyridazine ligand (pp) of the composition [Fe(pp)M(CN)4]∙G (where M = Pd, Pt; G = guest molecules) were obtained by a slow diffusion technique. A single-crystal X-ray analysis showed that both compounds adopted the structure of porous 3D frameworks, consisting of heterometallic cyano-bridged layers and interlayer pillar pp ligands, with a total solvent accessible volume of ca. 160 Å3 per iron(II) ion (about 37% of the unit cell volume). These frameworks displayed hysteretic SCO behaviour with T1/2 of 150/190 K (heating/cooling) for Pd complex and 135/170 K (heating/cooling) for Pt complex, which was confirmed by variable-temperature SCXRD experiments. This research shows the perspective of using pp ligand for building porous MOFs with spin transitions.

Keywords

• iron(II) complexes
• spin crossover
• porous coordination polymers
• metal-organic frameworks
• single-crystal X-ray diffraction