Strong electronic influence of equatorial ligands on frontier orbitals in paddlewheel dichromium(ii,ii) complexes
Strong electronic influence of equatorial ligands on frontier orbitals in paddlewheel dichromium(ii,ii) complexes
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赤道配体对叶轮二铬(ii,ii)配合物中前沿轨道的强电子影响
DOI：
10.1039/c8dt04347g
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发表时间：
2019
影响因子：
4
通讯作者：
Miyasaka Hitoshi
中科院分区：
文献类型：
--
作者：
Huang Po-Jung;Natori Yoshiki;Kitagawa Yasutaka;Sekine Yoshihiro;Kosaka Wataru;Miyasaka Hitoshi
合成了一系列取代苯甲酸根桥联的二价铬（II，II）配合物[Cr2（RCO 2）4（THF）2]（[Cr2]），其中RCO 2 −为取代苯甲酸根，并研究了其结构和磁性.还使用计算方法研究了轨道能以及磁耦合能。络合物的HOMO/LUMO能级强烈依赖于酸度，即，pKa，相应的苯甲酸（RCO 2 H），揭示了线性趋势，在相应的基团的非邻位，单邻位，和双邻位取代的基团。Cr <$Cr磁耦合常数（ES-T）受pKa影响很小;相反，ES-T与HOMO/LUMO能隙相关，并与Cr <$Cr距离密切相关。
A series of substituted benzoate-bridged dichromium(II,II) complexes [Cr2(RCO2)4(THF)2] ([Cr2]), where RCO2− is substituted benzoate, was synthesized and its structural and magnetic properties were investigated. The orbital energies, as well as magnetic coupling energies, were also investigated using computational approaches. The HOMO/LUMO energy levels of the complexes are strongly dependent on the acidity, i.e., pKa, of the corresponding benzoic acids (RCO2H), revealing a linear trend in the respective groups of non-ortho, mono-ortho, and bi-ortho substituted groups. The Cr⋯Cr magnetic coupling constant (ES–T) is little affected by pKa; instead, the ES–T is associated with the HOMO/LUMO gap and strongly correlated with the Cr⋯Cr distance.