DETERMINATION OF MAGNETIC AND STRUCTURAL-PROPERTIES IN SOLIDS CONTAINING ANTIFERROMAGNETICALLY COUPLED METAL CENTERS USING NMR METHODS - MAGNETO-STRUCTURAL CORRELATIONS IN ANHYDROUS COPPER(II) N-BUTYRATE
DETERMINATION OF MAGNETIC AND STRUCTURAL-PROPERTIES IN SOLIDS CONTAINING ANTIFERROMAGNETICALLY COUPLED METAL CENTERS USING NMR METHODS - MAGNETO-STRUCTURAL CORRELATIONS IN ANHYDROUS COPPER(II) N-BUTYRATE
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DOI：
10.1021/ic00294a007
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发表时间：
1988-10-19
影响因子：
4.6
通讯作者：
HAW, JF
中科院分区：
文献类型：
--
作者：
CAMPBELL, GC;HAW, JF
本文描述了一种研究含反铁磁耦合过渡金属中心的固体的磁结构关联的新方法，说明了核磁共振谱在这方面的潜力。本文报道了无水正丁酸铜[Cu(C3H7COO)2]2的变温(VT)~(13)C交叉极化魔角旋转(CP/MAS)核磁共振研究的结果。各向同性位移在起源时主要是接触的，对它们的温度依赖关系的统计分析允许计算单态-三态能级分离(-27)、抗磁位移(5dia)和电子-核超精细耦合常数(A)，这些结果揭示了电子沿超交换路径脱钙的机制。X-射线结晶学研究表明，化合物的结构与信号的多样性有关。标题化合物为三斜晶系，K=515.2(3)A3，a=9.035(2)α，b=5.192(2)A，c=11.695(3)A，a=85.88(2)，？=95.04(2)，Z=1，K=11.695(3)A3。
A new approach to the investigation of magneto-structuralcorrelations in solids containing antiferromagnetically coupled tran-sition-metal centers is described that illustrates the potential of NMR spectroscopy in such work. In this contribution we report the results of a variable-temperature (VT) 13C cross-polarization magic-angle-spinning (CP/MAS) NMR investigation of anhydrous copper (II) n-butyrate,[Cu (C3H7COO) 2] 2. Isotropic shifts are found to be primarily contact in origin, and a statistical analysis of their temperature dependence allows the calculation of singlet-triplet energy level separations (-27), diamagnetic shifts (5dia), and electron-nucleus hyperfine coupling constants (A), which are shown to give insightinto the mechanisms of electron delo-calization along the superexchange pathway. Signal multiplicity can be related to compound structure, which was determined by using X-ray crystallography. The title compound is triclinic and has a space group of P\with a= 9.035 (2) Á, b= 5.192 (2) A, c= 11.695 (3) A, a= 85.88 (2), ß= 95.04 (2), 7= 109.32 (2), Z= 1, and K= 515.2 (3) A3; the final weighted R value for 2169 reflections was 0.048.