Structural control of dithiazolyl radicals:: Case studies on 3′- and 4′-cyano-benzo-1,3,2-dithiazolyl, NCC6H3S2N
Structural control of dithiazolyl radicals:: Case studies on 3′- and 4′-cyano-benzo-1,3,2-dithiazolyl, NCC6H3S2N
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DOI：
10.1016/j.jorganchem.2006.12.020
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发表时间：
2007-06-01
影响因子：
2.3
通讯作者：
Rawson, Jeremy M.
中科院分区：
文献类型：
--
作者：
Alberola, Antonio;Burley, Jonathan;Rawson, Jeremy M.
具有π堆叠基序的二噻唑基自由基引起了特别的兴趣，因为它们能够通过固态相变在抗磁性扭曲π堆叠和顺磁性规则π堆叠结构之间表现出自旋切换。以前的研究表明，包括电负性杂原子到骨干有利于层状结构。该方法已推广到标题化合物4 ′-氰基苯并-1，3，2-二噻唑基（4-NCBDTA）的合成和表征。通过密度泛函理论计算、循环伏安法和电子顺磁共振谱研究了其电子结构，并通过室温下的X射线粉末衍射测定了其晶体结构。变温SQUID磁力测量表明4-NCBDTA经历了两次相变，每次都表现出双稳态;在室温下发生高温相变（T-C向下箭头= 291 K，T-C向上箭头= 304 K，Δ T = 13 K）;而低温相变发生在液氮温度以下（T-C向下箭头= 37 K，T-C向上箭头= 28 K; Δ T = 9 K）。(c)2007 Elsevier B. V.保留所有权利。
Dithiazolyl radicals with pi-stacking motifs have attracted particular interest because of their ability to exhibit spin-switching between diamagnetic distorted pi-stacks and paramagnetic regular pi-stacked structures through a solid state phase transition. Previous studies indicate that inclusion of electronegative heteroatoms into the backbone favours lamellar structures. This methodology has been extended to the synthesis and characterisation of the title compound, 4'-cyanobenzo-1,3,2-dithiazolyl (4-NCBDTA). Its electronic structure is probed through DFT calculations, cyclic voltammetry and EPR spectroscopy and its crystal structure determined by X-ray powder diffraction at room temperature. Variable temperature SQUID magnetometry reveals that 4-NCBDTA undergoes two phase transitions, each exhibiting bistability; a high temperature phase transition occurs at room temperature (T-C down arrow = 291 K, T-C up arrow = 304 K, Delta T = 13 K); whilst the low temperature phase transition occurs below liquid nitrogen temperatures (T-C down arrow = 37 K, T-C up arrow = 28 K; Delta T = 9 K). (c) 2007 Elsevier B.V. All rights reserved.