Strong metal-to-ligand charge transfer bands observed in Ni K- and L-edge XANES of planar Ni complexes
Strong metal-to-ligand charge transfer bands observed in Ni K- and L-edge XANES of planar Ni complexes
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DOI：
10.1107/s0909049599001338
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发表时间：
1999-05-01
影响因子：
2.5
通讯作者：
Kosugi, N
中科院分区：
文献类型：
--
作者：
Hatsui, T;Takata, Y;Kosugi, N
对具有低自旋3d(8)构型的平面Ni配合物K2Ni(CN)(4)的k边和l边XANES光谱进行了测量。H2O Ni(Hdmg)(2) （Hdmg: 2,3-丁二酮二氧基）和[(N - c4h9)(4)N](2)[Ni(mnt)(2)] （mnt: 1,2-二氰乙烯-1,2-二硫基）。在所有的光谱中，除了最低的Ni Is， 2p—>3d*原子线外，还发现了强卫星带。这些主要被分配到金属到配体的电荷转移（MLCT）过渡到具有优势配体pi*组分的未占据态，与从头算分子轨道预测很好地一致。在解释三维过渡金属化合物的金属k边和l边XANES时，低洼配体pi*轨道是必不可少的。
Polarized Ni K-edge and L-edge XANES spectra were measured for some planar Ni complexes with low-spin 3d(8) configuration, K2Ni(CN)(4). H2O Ni(Hdmg)(2) (Hdmg: 2,3-butanedione dioximato) and [(n-C4H9)(4)N](2)[Ni(mnt)(2)] (mnt: 1,2-dicyanovinylene-1,2-dithiolato). In all the spectra, strong satellite bands are found in addition to the lowest Ni Is, 2p-->3d* atomic lines. These an mostly assigned to the metal-to-ligand charge transfer (MLCT) transitions to unoccupied states with dominant ligand pi* components, in good agreement with ab initio molecular orbital predictions. The low-lying ligand pi* orbital is essential in interpreting the metal K-edge and L-edge XANES of 3d transition metal compounds.