Thermally and Photoinduced Spin-Crossover Behavior in Iron(II)–Silver(I) Cyanido-Bridged Coordination Polymers Bearing Acetylpyridine Ligands
Carlos Cruz, Jorge Galdames, Liz Camayo-Gutierrez, Mathieu Rouzières, Corine Mathonière, Nieves Menéndez, Nathalie Audebrand, Sebastian E. Reyes‐Lillo, Rodolphe Clérac, Diego Venegas‐Yazigi, Verónica Paredes‐García
Abstract
We report two new cyanido-bridged Fe(II)–Ag(I) coordination polymers using different acetylpyridine isomers, {Fe(4acpy) 2 [Ag(CN) 2 ] 2 } 1 and {Fe(3acpy)[Ag(CN) 2 ] 2 } 2 (4acpy = 4-acetylpyridine; 3acpy = 3-acetylpyridine) displaying thermally and photoinduced spin crossover (SCO). In both cases, the acetylpyridine ligand directs the coordination polymer structure and the SCO of the materials. Using 4-acetylpyridine, a two-dimensional (2D) structure is observed in 1 made of layers stacked on each other by silver–ketone interactions leading to a complete SCO and reversible thermally and photoswitching of the magnetic and optical properties. Changing the acetyl group to a 3-position, a completely different structure is obtained for 2 . The unexpected coordination of the carbonyl group to the Fe(II) centers induces a three-dimensional (3D) structure, leading to statistical disorder around the Fe(II) with three different coordination spheres, [N 6 ], [N 4 O 2 ], and [N 5 O]. This disorder gives rise to an incomplete thermally induced SCO with a poor photoswitchability. These results demonstrate that the choice of the acetyl position on the pyridine dictates the structural characteristics of the compounds with a direct impact on the SCO behavior. Remarkably, this work opens interesting perspectives for the future design of Fe–Ag cyanido coordination polymers with judiciously substituted pyridine ligands to tune the thermally and photoinduced SCO properties.