Structural, magnetic, and electronic properties of phenolic oxime complexes of Cu and Ni.
Structural, magnetic, and electronic properties of phenolic oxime complexes of Cu and Ni.
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DOI：
10.1021/ic2020644
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发表时间：
2011-11
影响因子：
4.6
通讯作者：
Alexander M. Whyte;Benjamin D. Roach;David K. Henderson;P. A. Tasker;M. Matsushita;K. Awaga;Fraser J. White;Patricia R. Richardson;N. Robertson
中科院分区：
文献类型：
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作者：
Alexander M. Whyte;Benjamin D. Roach;David K. Henderson;P. A. Tasker;M. Matsushita;K. Awaga;Fraser J. White;Patricia R. Richardson;N. Robertson
本文合成了Ni（L（1））（2），Ni（L（2））（2），Cu（L（1））（2），Cu（L（2））（2）四种四方平面配合物，其中L（1）H = 2-羟基-5-叔辛基苯乙酮肟，L（2）H = 2-羟基-5-正丙基苯乙酮肟。密度泛函理论（DFT）和时间相关的DFT（TDDFT）计算，以及在顺磁性物质的情况下，电子顺磁共振（EPR）和磁化率。在M（L（1））（2）（M = Ni，Cu）的晶体结构中，烷基从叔辛基到正丙基的变化使配合物的电子隔离成为可能，而M（L（2））（2）（M = Ni，Cu）的π堆积作用则相反。Cu（L（2））（2）的一维反铁磁链证明了这一点，但Cu（L（1））（2）在1.8 K下具有理想的顺磁行为。尽管M（L（2））（2）具有同构单晶结构，但薄膜X射线衍射和扫描电子显微镜（SEM）显示出不同的形态，这取决于金属和沉积方法（气相或溶液）。铜配合物显示有限的电子之间的相互作用的中心金属和离域配体，与更多的混合的情况下，镍（II），如电化学和紫外/维斯光谱。配合物M（L（2））（2）在场效应晶体管（FET）器件中显示出差的电荷传输，尽管能够形成π-堆叠结构，这为用于导电薄膜器件的金属配合物提供了设计见解。
Square planar complexes of the type Ni(L(1))(2), Ni(L(2))(2), Cu(L(1))(2), and Cu(L(2))(2), where L(1)H = 2-hydroxy-5-t-octylacetophenone oxime and L(2)H = 2-hydroxy-5-n-propylacetophenone oxime, have been prepared and characterized by single-crystal X-ray diffraction, cyclic voltammetry, UV/vis spectroscopy, field-effect-transistor measurements, density functional theory (DFT) and time-dependent DFT (TDDFT) calculations, and, in the case of the paramagnetic species, electron paramagnetic resonance (EPR) and magnetic susceptibility. Variation of alkyl groups on the ligand from t-octyl to n-propyl enabled electronic isolation of the complexes in the crystal structures of M(L(1))(2) contrasting with π-stacking interactions for M(L(2))(2) (M = Ni, Cu). This was evidenced by a one-dimensional antiferromagnetic chain for Cu(L(2))(2) but ideal paramagnetic behavior for Cu(L(1))(2) down to 1.8 K. Despite isostructural single crystal structures for M(L(2))(2), thin-film X-ray diffraction and scanning electron microscopy (SEM) revealed different morphologies depending on the metal and the deposition method (vapor or solution). The Cu complexes displayed limited electronic interaction between the central metal and the delocalized ligands, with more mixing in the case of Ni(II), as shown by electrochemistry and UV/vis spectroscopy. The complexes M(L(2))(2) showed poor charge transport in a field-effect transistor (FET) device despite the ability to form π-stacking structures, and this provides design insights for metal complexes to be used in conductive thin-film devices.