Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, USA.
Inorg Chem. 2011 Jul 4;50(13):6347-52. doi: 10.1021/ic2008039. Epub 2011 Jun 6.
We employed infrared spectroscopy along with complementary lattice dynamics and spin density calculations to investigate pressure-driven local structure distortions in the copper coordination polymer Cu(pyz)F(2)(H(2)O)(2). Here, pyz is pyrazine. Our study reveals rich and fully reversible local lattice distortions that buckle the pyrazine ring, disrupt the bc-plane O-H···F hydrogen-bonding network, and reinforce magnetic property switching. The resiliency of the soft organic ring is a major factor in the stability of this material. Interestingly, the collective character of the lattice vibrations masks direct information on the Cu-N and Cu-O linkages through the series of pressure-induced Jahn-Teller axis switching transitions, although Cu-F bond softening is clearly identified above 3 GPa. These findings illustrate the importance of combined bulk and local probe techniques for microscopic structure determination in complex materials.
我们采用红外光谱学以及补充的晶格动力学和自旋密度计算，研究了在铜配位聚合物 Cu(pyz)F(2)(H(2)O)(2) 中压力驱动的局部结构扭曲。这里，pyz 是吡嗪。我们的研究揭示了丰富而完全可逆的局部晶格扭曲，这些扭曲使吡嗪环弯曲，破坏 bc 面 O-H···F 氢键网络，并增强磁性能切换。软有机环的弹性是该材料稳定性的主要因素。有趣的是，晶格振动的集体特征通过一系列压力诱导的 Jahn-Teller 轴切换跃迁掩盖了关于 Cu-N 和 Cu-O 键的直接信息，尽管在超过 3 GPa 时明显识别到 Cu-F 键软化。这些发现说明了在复杂材料中进行微观结构确定时，结合体相和局部探针技术的重要性。
