Phase Transitions, Crystal Structures, and Magnetic Properties of Ferrocenium Ionic Plastic Crystals with CF3BF3 and Other Anions
Phase Transitions, Crystal Structures, and Magnetic Properties of Ferrocenium Ionic Plastic Crystals with CF3BF3 and Other Anions
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DOI：
10.1002/slct.201900141
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发表时间：
2019-01-31
期刊：
影响因子：
2.1
通讯作者：
Mochida, Tomoyuki
中科院分区：
文献类型：
--
作者：
Kimata, Hironori;Sakurai, Takahiro;Mochida, Tomoyuki
阳离子夹心复合物的盐通常表现出离子塑性相;然而，只有少数在室温下表现出塑性相。为了探索使用CF 3BF 3阴离子来降低向塑性相的转变温度，我们制备了CF 3BF 3与各种二茂铁衍生物的盐，[D][CF 3BF 3]（D=FeCp*（2），Fe（C5 Me 4 H）（2），Fe（C5 H4 Me）（2），FeCp（C5 H4 Me），FeCp 2; Cp*= C5 Me 5，Cp= C5 H5）。虽然[FeCp*（2）][CF 3BF 3]在417 K以上表现出塑性相，但其他盐形成室温离子塑性晶体，在266-291 K范围内相变为塑性相。[FeCp 2][OTf]的晶体结构和热性能进行了阐述比较。此外，合成了具有其他阴离子的十甲基二茂铁盐，并对其结构进行了表征：[FeCp*（2）][X]（X=N（SO 2F）（2）和B（CN）（4））在400 K以上表现出向塑性相的相变，而含碳硼烷的盐[FeCp*（2）]（2）[B12 F12]和[FeCp*（2）][Co（C2B 9 H11）（2）]没有表现出塑性相。
Salts of cationic sandwich complexes often exhibit an ionic plastic phase; however, only a few exhibit a plastic phase at room temperature. To explore the use of the CF3BF3 anion to lower the transition temperature to the plastic phase, we prepared salts of CF3BF3 with various ferrocene derivatives, [D][CF3BF3] (D=FeCp*(2), Fe(C5Me4H)(2), Fe(C5H4Me)(2), FeCp(C5H4Me), FeCp2; Cp*=C5Me5, Cp=C5H5). Although [FeCp*(2)][CF3BF3] exhibited a plastic phase above 417 K, the other salts formed room-temperature ionic plastic crystals with a phase transition to the plastic phase in the range 266-291 K. The crystal structure and thermal properties of [FeCp2][OTf] were elucidated for comparison. In addition, decamethylferrocenium salts with other anions were synthesized and structurally characterized: [FeCp*(2)][X] (X=N(SO2F)(2) and B(CN)(4)) exhibited a phase transition to the plastic phase above 400 K, whereas carborane-containing salts [FeCp*(2)](2)[B12F12] and [FeCp*(2)][Co(C2B9H11)(2)] did not exhibit a plastic phase.