Biological Sciences Division, Pacific Northwest National Laboratory, 902 Battlelle Boulevard, Richland, Washington 99352, United States, USA.
J Am Chem Soc. 2010 Dec 1;132(47):16727-9. doi: 10.1021/ja1054252. Epub 2010 Nov 8.
We have examined the antiferromagneticly coupled bis(μ-oxo)dimanganese(IV) complex [Mn(2)O(2)(salpn)(2)] (1) with (55)Mn solid-state NMR at cryogenic temperatures and first-principle theory. The extracted values of the (55)Mn quadrupole coupling constant, C(Q), and its asymmetry parameter, η(Q), for 1 are 24.7 MHz and 0.43, respectively. Further, there was a large anisotropic contribution to the shielding of each Mn(4+), i.e. a Δσ of 3375 ppm. Utilizing broken symmetry density functional theory, the predicted values of the electric field gradient (EFG) or equivalently the C(Q) and η(Q) at ZORA, PBE QZ4P all electron level of theory are 23.4 MHz and 0.68, respectively, in good agreement with experimental observations.
我们已经使用低温下的 (55)Mn 固态 NMR 和第一性原理理论研究了反铁磁耦合的双(μ-氧)二锰(IV)配合物[Mn2O2(salpn)2]（1）。1 的 (55)Mn 四极耦合常数 C(Q)和其不对称参数 η(Q)的提取值分别为 24.7 MHz 和 0.43。此外，每个 Mn(4+)的屏蔽存在很大的各向异性贡献，即 Δσ 为 3375 ppm。利用非对称密度泛函理论，在 ZORA、PBE QZ4P 全电子理论水平下预测的电场梯度 (EFG)或等效的 C(Q)和 η(Q)值分别为 23.4 MHz 和 0.68，与实验观测结果吻合较好。
