Cooperative High-Temperature Spin Crossover Accompanied by a Highly Anisotropic Structural Distortion

被引:48
|
作者
Gural'skiy, Il'ya A. [1 ,2 ]
Golub, Bohdan O. [1 ]
Shylin, Sergii I. [1 ,2 ]
Ksenofontov, Vadim [2 ]
Shepherd, Helena J. [3 ]
Raithby, Paul R. [3 ]
Tremel, Wolfgang [2 ]
Fritsky, Igor O. [1 ]
机构
[1] Taras Shevchenko Natl Univ Kyiv, Dept Chem, Volodymyrska St 64, UA-01601 Kiev, Ukraine
[2] Johannes Gutenberg Univ Mainz, Inst Inorgan & Analyt Chem, Staudingerweg 9, D-55099 Mainz, Germany
[3] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England
基金
英国工程与自然科学研究理事会;
关键词
Metal-organic frameworks; Spin crossover; Cooperative effects; Magnetic properties; Iron; NEGATIVE THERMAL-EXPANSION; METAL-ORGANIC FRAMEWORKS; ROOM-TEMPERATURE; TRANSITION-TEMPERATURE; COORDINATION POLYMER; NANOPARTICLES; HYSTERESIS; GUEST; STATE; BISTABILITY;
D O I
10.1002/ejic.201600406
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Spin transitions are a spectacular example of molecular switching that can provoke extreme electronic and structural reorganizations in coordination compounds. A new 3D cyanoheterometallic framework, [Fe(pz){Au(CN)(2)}(2)], has been synthesized in which a highly cooperative spin crossover has been observed at 367 and 349 K in heating and cooling modes, respectively. Mossbauer spectroscopy revealed a complete transition between the diamagnetic and paramagnetic states of the iron centres. The low-spin-to-high-spin transition induced a drastic structural distortion involving a large one-directional expansion (ca. 10.6%) and contraction (ca. 9.6%) of the lattice. Negative thermal expansion along the c axis was detected below and above the transition temperature.
引用
收藏
页码:3191 / 3195
页数:5
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