Solid-state (55)Mn NMR spectroscopy of bis(μ-oxo)dimanganese(IV) [Mn(2)O(2)(salpn)(2)], a model for the oxygen evolving complex in photosystem II.
Solid-state (55)Mn NMR spectroscopy of bis(μ-oxo)dimanganese(IV) [Mn(2)O(2)(salpn)(2)], a model for the oxygen evolving complex in photosystem II.
复制标题
双(μ-oxo)dimanganese(IV) [Mn(2)O(2)(salpn)(2)]的固态(55)Mn NMR光谱，是光系统II中析氧复合物的模型。
DOI：
10.1021/ja1054252
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发表时间：
2010
影响因子：
15
通讯作者：
Lipton,AndrewS
中科院分区：
文献类型：
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作者：
Ellis,PaulD;Sears,JesseA;Yang,Ping;Dupuis,Michel;Boron3rd,ThaddeusT;Pecoraro,VincentL;Stich,TroyA;Britt,RDavid;Lipton,AndrewS
本文用第一性原理和低温~（55）Mn固体核磁共振谱研究了反铁磁耦合的双（μ-氧代）二锰（IV）配合物[Mn_2 O_2（salpn）_2]（1）。对1的55 Mn四极耦合常数CQ和非对称参数ηQ的提取值分别为24.7MHz和0.43。此外，存在对每个Mn 4+的屏蔽的大的各向异性贡献，即3375 ppm的Δσ。利用对称性破缺密度泛函理论，计算了在ZORA、PBE QZ 4P全电子能级上的电场梯度（EFG）或等效的CQ和η Q，分别为23.4MHz和0.68，与实验结果符合较好.
We have examined the antiferromagneticly coupled bis(μ-oxo)dimanganese(IV) complex [Mn2O2(salpn)2] (1) with55Mn solid-state NMR at cryogenic temperatures and first-principle theory. The extracted values of the55Mn quadrupole coupling constant,CQ, and its asymmetry parameter, ηQ, for1are 24.7 MHz and 0.43, respectively. Further, there was a large anisotropic contribution to the shielding of each Mn4+, i.e. a Δσ of 3375 ppm. Utilizing broken symmetry density functional theory, the predicted values of the electric field gradient (EFG) or equivalently theCQand ηQat ZORA, PBE QZ4P all electron level of theory are 23.4 MHz and 0.68, respectively, in good agreement with experimental observations.