Lability-Controlled Syntheses of Heterometallic Clusters
Lability-Controlled Syntheses of Heterometallic Clusters
复制标题
DOI：
10.1002/anie.201309374
复制
发表时间：
2014-03-10
影响因子：
16.6
通讯作者：
Oshio, Hiroki
中科院分区：
文献类型：
--
作者：
Newton, Graham N.;Mitsumoto, Kiyotaka;Oshio, Hiroki
使用庞大的双齿配体来稳定大环[（Fe 8 Co 6 II）-Co-III]簇。通过用一个或两个甲氧基衍生化来调节配体的碱性，分别导致了同源[（Fe 8 Co 6 II）-Co-III]物种和[（Fe 6 Fe 2Co 2Co 2 II）-Fe-III-Co-II-Co-III]络合物的分离。降低反应温度允许分离具有所有三个配体的[（Fe 6 Fe 2Co 2Co 2 II）-Fe-III-Co-II-Co-III]簇。铁/镍体系的变温吸收数据和相应的实验表明，铁/钴自组装过程受溶液态电子转移耦合自旋跃迁（ETCST）的发生及其对反应中间体不稳定性的影响.
A bulky bidentate ligand was used to stabilize a macrocyclic [(Fe8Co6II)-Co-III] cluster. Tuning the basicity of the ligand by derivatization with one or two methoxy groups led to the isolation of a homologous [(Fe8Co6II)-Co-III] species and a [(Fe6Fe2Co2Co2II)-Fe-III-Co-II-Co-III] complex, respectively. Lowering the reaction temperatures allowed isolation of [(Fe6Fe2Co2Co2II)-Fe-III-Co-II-Co-III] clusters with all three ligands. Temperature-dependent absorption data and corresponding experiments with iron/nickel systems indicated that the iron/cobalt self-assembly process was directed by the occurrence of solution-state electron-transfer-coupled spin transition (ETCST) and its influence on reaction intermediate lability.