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Nanoporosity, Inclusion Chemistry, and Spin Crossover in Orthogonally Interlocked Two-Dimensional Metal-Organic Frameworks

机译:正交互锁的二维金属-有机骨架中的纳米孔隙度,包含化学和自旋交叉

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摘要

[Fe(tvp)(2)(NCS)(2)] (1) (tvp=trans-(4,4-vinylenedipyridine)) consists of two independent perpendicular stacks of mutually interpenetrated two-dimensional grids. This uncommon supramolecular conformation defines square-sectional nanochannels (diagonal approximate to 2.2nm) in which inclusion molecules are located. The guest-loaded framework 1@guest displays complete thermal spin-crossover (SCO) behavior with the characteristic temperature T-1/2 dependent on the guest molecule, whereas the guest-free species 1 is paramagnetic whatever the temperature. For the benzene-guest derivatives, the characteristic SCO temperature T-1/2 decreases as the Hammet sigma(p) parameter increases. In general, the 1@guest series shows large entropy variations associated with the SCO and conformational changes of the interpenetrated grids that leads to a crystallographic-phase transition when the guest is benzonitrile or acetonitrile/H2O.
机译:[Fe(tvp)(2)(NCS)(2)](1)(tvp =反式-(4,4-亚乙烯基二吡啶))由相互渗透的二维网格的两个独立的垂直堆栈组成。这种罕见的超分子构象定义了包含分子位于其中的正方形截面纳米通道(对角线近似于2.2nm)。客体框架1 @ guest会显示完整的热自旋交叉(SCO)行为,其特征温度T-1 / 2取决于客体分子,而无客体物种1在任何温度下都是顺磁性的。对于苯客体衍生物,随着Hammet sigma(p)参数增加,特征SCO温度T-1 / 2降低。通常,1Guest系列显示出与SCO相关的大的熵变化以及互穿网格的构象变化,当客体是苄腈或乙腈/ H2O时,这会导致结晶相变。

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