A New Systematic Construction of Novel Three-Dimensional Spin Crossover Coordination Polymers Based on the [AgI 2(CN)3] Building Unit

ACS Omega. 2021 Apr 29;6(18):12187-12193. doi: 10.1021/acsomega.1c00892. eCollection 2021 May 11.

Abstract

New three-dimensional spin crossover (SCO) coordination polymers systematically constructed by the novel building unit [AgI 2(CN)3], FeII(3-Br-5-CH3pyridine)2[AgI 2(CN)3][AgI(CN)2] (1), FeII(3-Br-5-Clpyridine)2[AgI 2(CN)3][AgI(CN)2] (2), and FeII(3,5-Brpyridine)2[AgI 2(CN)3][AgI(CN)2] (3), have been synthesized and characterized. The bismonodentate binuclear [Ag2(CN)3]- and mononuclear [AgI(CN)2]- units and FeII atoms assemble to form a 3D network structure. The structures of 1-3 are crystallographically identical, which made up the triply interpenetration combined with complicated intermolecular interactions including Ag···Ag, Ag···X (pyridine substituents) and π-stacking interactions. Magnetic and differential scanning calorimetry studies were performed for 1-3. These compounds display a similar SCO behavior, while the critical temperatures (T c) are shifted by the substituent effect. Due to the identical structures of 1-3, the order of T c clearly corresponds with the Hammett constant.