Wang Di, Zhang Ren, Liu Jin, Ji Bibi, Wang Wenping, Peng Mengyuan, Huang Chen, Cheng Lizhuoran, Ding Yi
School of Materials and Chemical Engineering, Anhui Jianzhu University, Hefei 230601, China.
School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei 230009, China.
Polymers (Basel). 2023 May 18;15(10):2363. doi: 10.3390/polym15102363.
A novel one-dimensional malleable spin-crossover (SCO) complex {Fe(MPEG-trz)} has been successfully synthesized by molecular self-assembly between 4-amino-1,2,4-triazoles (MPEG-trz) grafted with a long flexible chain methoxy polyethylene glycol (MPEG) and metallic complex Fe(BF)•6HO. The detailed structure information was illustrated by using FT-IR and H NMR measurements, while the physical behaviors of the malleable SCO complexes were systematically investigated by using magnetic susceptibility measurements using superconductivity quantum interference device (SQUID) and differential scanning calorimetry (DSC). This new metallopolymer exhibits a remarkable spin crossover transition behavior, between two spin quantum states (Fe ions): high spin (HS) state (quintet state) and low spin (LS) state (singlet state), at a specific critical temperature with a slender hysteresis loop of 1 K. DFT computations revealed the partial rules of HOMO-LUMO energy levels and spin density distributions of different four-position substituted [Fe(1,2,4-triazole)] derivatives with different length of repeat units in polymer complexes. This can go a step further to depict the spin and magnetic transition behaviors of SCO polymer complexes. Furthermore, the coordination polymers possess an excellent processability due to an outstanding malleability, which can be easily shaped into a polymer film with spin magnetic switching properties.
通过接枝长柔性链甲氧基聚乙二醇（MPEG）的4-氨基-1,2,4-三唑（MPEG-trz）与金属配合物Fe(BF)•6H₂O之间的分子自组装，成功合成了一种新型一维可延展自旋交叉（SCO）配合物{Fe(MPEG-trz)}。通过傅里叶变换红外光谱（FT-IR）和¹H核磁共振（¹H NMR）测量说明了详细的结构信息，同时利用超导量子干涉装置（SQUID）和差示扫描量热法（DSC）进行磁化率测量，系统地研究了可延展SCO配合物的物理行为。这种新型金属聚合物在特定临界温度下，在两个自旋量子态（铁离子）：高自旋（HS）态（五重态）和低自旋（LS）态（单重态）之间表现出显著的自旋交叉转变行为，具有1 K的细长滞后回线。密度泛函理论（DFT）计算揭示了聚合物配合物中不同四位置取代的[Fe(1,2,4-三唑)]衍生物具有不同重复单元长度时的最高占据分子轨道（HOMO）-最低未占据分子轨道（LUMO）能级和自旋密度分布的部分规律。这可以进一步描绘SCO聚合物配合物的自旋和磁转变行为。此外，由于具有出色的延展性，配位聚合物具有优异的加工性能，可以很容易地成型为具有自旋磁开关特性的聚合物薄膜。
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