名义高价镍三核配合物的电荷转移效应
The Prominent Charge-Transfer Effects of Trinuclear Complexes with Nominally High Nickel Valences
摘要：
最近合成的Rh-Ni三核配合物3-氨基硫醇（apt）金属配体[Ni{Rh（apt）$_{3}$ } $_{2}$ ]（NO $_{3}$）$_{n}$（$n$ = 2，3，4）与硫离子六配位，被发现在名义Ni $^{2+}$和Ni $^{4+}$态之间具有化学互变.为了从物理角度阐明它们的相互转化性质的起源和四价高氧化态的稳定性，我们用软X射线芯能级吸收光谱（XAS）系统地研究了[Ni{Rh（apt）$_{3}$ } $_{2}$ ]（NO $_{3}$）$_{n}$的局域3 $d$电子结构.通过单中心组态相互作用团簇模型模拟再现了实验数据，结果表明，$n=3,4$的电荷转移组态比名义的$d$ -电子数组态更稳定，导致了显著的电荷转移效应.这些也由[Ni{Rh（apt）$_{3}$ } $_{2}$ ]（NO $_{3}$）$_{n}$的S $K$ -边缘XAS支持。我们的研究结果表明，所发现的电荷转移效应有一个关键的作用，实现相互转换的性质，以及高氧化态的镍离子的稳定性。
英文摘要：
Recently synthesized Rh-Ni trinuclear complexes hexacoordinated with sulfur ions, 3-aminopropanethiolate (apt) metalloligand [Ni{Rh(apt)$_{3}$}$_{2}$](NO$_{3}$)$_{n}$ ($n$ = 2, 3, 4), are found to be chemically interconvertible between the nominal Ni$^{2+}$ and Ni$^{4+}$ states. In order to clarify the origins of their interconvertible nature and the stability of such a high oxidation state as the tetravalency from the physical point of view, we have systematically investigated the local 3$d$ electronic structures of [Ni{Rh(apt)$_{3}$}$_{2}$](NO$_{3}$)$_{n}$ by means of soft X-ray core-level absorption spectroscopy (XAS). The experimental data have been reproduced by the single-site configuration-interaction cluster-model simulations, which indicate that the charge-transferred configurations are more stable than the nominal $d$-electron-number configuration for $n=3,4$ leading to the prominent charge-transfer effects. These are also supported by S $K$-edge XAS of [Ni{Rh(apt)$_{3}$}$_{2}$](NO$_{3}$)$_{n}$. Our results imply that the found charge-transfer effects have a key role to realize the interconvertible nature as well as the stability of the high oxidization state of the Ni ions.
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