当前位置：
X-MOL 学术
›
Inorg. Chem.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Long-Range Ferromagnetic Exchange Interactions Mediated by Mn-CeIV-Mn Superexchange Involving Empty 4f Orbitals.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-06-23 , DOI: 10.1021/acs.inorgchem.0c00332 Sayak Das Gupta 1 , Robert L Stewart 2 , Dian-Teng Chen 3 , Khalil A Abboud 1 , Hai-Ping Cheng 3 , Stephen Hill 2 , George Christou 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-06-23 , DOI: 10.1021/acs.inorgchem.0c00332 Sayak Das Gupta 1 , Robert L Stewart 2 , Dian-Teng Chen 3 , Khalil A Abboud 1 , Hai-Ping Cheng 3 , Stephen Hill 2 , George Christou 1
Affiliation
|
Reactions involving reductive aggregation of MnO4– in methanol in the presence of CeIV and an excess of carboxylic acid have led to the synthesis of structurally related Ce/Mn clusters, [Ce3Mn5O8(OMe)(O2CBut)13(MeOH)] (1) and [Ce2Mn3O5(O2CPh)9(MeOH)3] (2), containing at least one {Mn2Ce2O4} cubane unit. The cores of both clusters contain Mnx units separated by three (1) or two (2) CeIV ions. Fits of variable-temperature, solid-state dc and ac magnetic susceptibility data reveal dominant ferromagnetic interactions within 1 and 2, resulting in the maximum S = 17/2 and S = 5 ground state spins, respectively, and thus suggesting significant ferromagnetic (F) interactions between the Mnx units that are ≥6 Å apart and separated by four intervening bonds through diamagnetic CeIV. Fits of magnetic susceptibility data also revealed unusual long-range F interactions, and this finding was further supported by high-field EPR measurements and simulations. Density functional theory calculations and a Wannier function analysis confirm long-range interactions and indicate a Mn–Ce–Mn superexchange pathway via Mn-d/Ce-f orbital overlap/hybridization
中文翻译：
由涉及空的4f轨道的Mn-CeIV-Mn超交换介导的远距离铁磁交换相互作用。
涉及的MnO还原聚合反应4 -在甲醇中的Ce的存在IV和过量羧酸的已导致结构上相关的Ce / Mn为簇的合成，[CE 3的Mn 5 ø 8（OME）（O 2 CBU吨）13（MeOH）]（1）和[Ce 2 Mn 3 O 5（O 2 CPh）9（MeOH）3 ]（2），包含至少一种{Mn 2 Ce 2 O 4古巴单位。两个簇的核心都包含被三（1）或两（2）Ce IV离子隔开的Mn x单元。变温的配合，固态直流和交流磁化率数据揭示内主导铁磁相互作用1和2，从而在最大小号= 17 / 2和小号= 5基态自旋，分别和从而表明显著铁磁（F ）间隔≥6Å的Mn x单元之间的相互作用，并通过抗磁性Ce IV被四个中间键隔开。磁化率数据的拟合还显示了异常的远距离F相互作用，这一发现得到高场EPR测量和模拟的进一步支持。密度泛函理论计算和Wannier函数分析证实了长程相互作用，并通过Mn-d / Ce-f轨道重叠/杂交表明了Mn-Ce-Mn超交换途径
更新日期：2020-07-06
中文翻译：
由涉及空的4f轨道的Mn-CeIV-Mn超交换介导的远距离铁磁交换相互作用。
涉及的MnO还原聚合反应4 -在甲醇中的Ce的存在IV和过量羧酸的已导致结构上相关的Ce / Mn为簇的合成，[CE 3的Mn 5 ø 8（OME）（O 2 CBU吨）13（MeOH）]（1）和[Ce 2 Mn 3 O 5（O 2 CPh）9（MeOH）3 ]（2），包含至少一种{Mn 2 Ce 2 O 4古巴单位。两个簇的核心都包含被三（1）或两（2）Ce IV离子隔开的Mn x单元。变温的配合，固态直流和交流磁化率数据揭示内主导铁磁相互作用1和2，从而在最大小号= 17 / 2和小号= 5基态自旋，分别和从而表明显著铁磁（F ）间隔≥6Å的Mn x单元之间的相互作用，并通过抗磁性Ce IV被四个中间键隔开。磁化率数据的拟合还显示了异常的远距离F相互作用，这一发现得到高场EPR测量和模拟的进一步支持。密度泛函理论计算和Wannier函数分析证实了长程相互作用，并通过Mn-d / Ce-f轨道重叠/杂交表明了Mn-Ce-Mn超交换途径
京公网安备 11010802027423号