Chemical/Physical pressure tunable spin-transition temperature and hysteresis in a two-step spin crossover porous coordination framework |
| |
Authors: | Jian-Bin Lin Wei Xue Bao-Ying Wang Jun Tao Wei-Xiong Zhang Jie-Peng Zhang Xiao-Ming Chen |
| |
Institution: | MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University , Guangzhou 510275, China. |
| |
Abstract: | 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 Fe(II)N(6) 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 P2(1)/n for all high-spin Fe(II), to P1? for ordered half high-spin and half low-spin Fe(II), and back to P2(1)/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. |
| |
Keywords: | |
本文献已被 PubMed 等数据库收录! |
|