Two-dimensional iron(II) spin crossover complex constructed of bifurcated NH•••O- hydrogen bonds and π-π interactions:: [FeII(HLH,Me)2](ClO4)2•1.5MeCN (HLH,Me = imidazol-4-yl-methylidene-8-amino-2-methylquinoline)
Two-dimensional iron(II) spin crossover complex constructed of bifurcated NH•••O- hydrogen bonds and π-π interactions:: [FeII(HLH,Me)2](ClO4)2•1.5MeCN (HLH,Me = imidazol-4-yl-methylidene-8-amino-2-methylquinoline)
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DOI：
10.1021/ic061960a
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发表时间：
2007-04-16
影响因子：
4.6
通讯作者：
Iijima, Seiichiro
中科院分区：
文献类型：
--
作者：
Hagiwara, Hiroaki;Hashimoto, Shingo;Iijima, Seiichiro
合成了一个二维铁（II）自旋交叉配合物[Fe-II（HLH，Me）（2）]（ClO 4）（2）中心点1.5MeCN（1），其中HLH，Me =咪唑-4-亚甲基-8-氨基-2-甲基喹啉。1在从5到350 K的第一次升温过程中，HS（S = 2）和LS（S = 0）状态之间从180到325 K的逐渐自旋转变，其中去除1.5MeCN，并且在从350到5 K的第一次冷却过程中，在T-1/2向下箭头= 174 K处存在突然的自旋转变。在第一个循环之后，该化合物在T-1/2向上箭头= 185 K和T-1/2向下箭头= 174 K处显示出突然的自旋转变，在第二个循环中具有11 K宽的滞后。1的晶体结构在296（HS和LS态之间的中间态）和150 K（LS态）下测定。该结构由[Fe-II（HLH，Me）（2）]（2+）阳离子的两个相邻咪唑NH基团与两个ClO ~（4-）离子之间的分叉NH中心点中心点O-氢键以及两个相邻阳离子的两个喹啉环之间的π-π相互作用构成的二维扩展结构组成。热重分析表明，即使在室温下，溶剂分子也会逐渐消失，并在369 K下完全消失。去溶剂化的配合物1'在T-1/2向上箭头= 180 K和T-1/2向下箭头= 174 K处显示出突变的自旋转变，具有6 K宽的滞后。
A 2D iron(II) spin crossover complex, [Fe-II(HLH,Me)(2)](ClO4)(2)center dot 1.5MeCN (1), was synthesized, where HLH,Me = imidazol-4-yl-methylidene-8-amino-2-methylquinoline. 1 showed a gradual spin transition between the HS (S = 2) and LS (S = 0) states from 180 to 325 K within the first warming run from 5 to 350 K, in which 1.5MeCN is removed, and there was an abrupt spin transition at T-1/2 down arrow = 174 K in the first cooling run from 350 to 5 K. Following the first cycle, the compound showed an abrupt spin transition at T-1/2 up arrow = 185 K and T-1/2 down arrow = 174 K with 11 K wide hysteresis in the second cycle. The crystal structures of 1 were determined at 296 (an intermediate between the HS and LS states) and 150 K (LS state). The structure consists of a 2D extended structure constructed of both the bifurcated NH center dot center dot center dot O- hydrogen bonds between two ClO4- ions and two neighboring imidazole NH groups of the [Fe-II(HLH,Me)(2)](2+) cations and the pi-pi interactions between the two quinolyl rings of the two adjacent cations. Thermogravimetric analysis showed that solvent molecules are gradually eliminated even at room temperature and completely removed at 369 K. Desolvated complex 1' showed an abrupt spin transition at T-1/2 up arrow = 180 K and T-1/2 down arrow = 174 K with 6 K wide hysteresis.