Probing Edge/Support Electronic Cooperativity in Single Edge Fe/Co 6 Se 8 Clusters
Probing Edge/Support Electronic Cooperativity in Single Edge Fe/Co 6 Se 8 Clusters
复制标题
探测单边缘 Fe/Co 6 Se 8 团簇中的边缘/支持电子协同性
DOI：
10.1021/acs.inorgchem.3c01661
复制
发表时间：
2023
影响因子：
4.6
通讯作者：
Velian, Alexandra
中科院分区：
文献类型：
--
作者：
Mitchell, Benjamin S.;Chirila, Andrei;Anderton, Kevin J.;Kaminsky, Werner;Velian, Alexandra
这项研究提供了一个原子级精确的Fe/Co 6Se 8簇的电子结构和Fe活性位点和非无辜的Co 6Se 8支持之间的氧化还原协同性的程度的见解。化学氧化研究使两种类型的氧化Fe/Co 6Se 8集群的隔离，其中的counterparts（I-或OTf-）的性质显着影响Fe和Co 6Se 8单元之间的结构相互作用。通过单晶X射线衍射、57 Fe Mo穆斯堡尔谱和31 P {1 H} NMR谱的实验表征由计算分析补充。总的来说，研究表明，氧化后，Fe边缘网站和Co 6Se 8核心之间共享的电荷。
This study provides insights into the electronic structure of an atomically precise Fe/Co6Se8cluster and the extent of redox cooperativity between the Fe active site and the noninnocent Co6Se8support. Chemical oxidation studies enable the isolation of two types of oxidized Fe/Co6Se8clusters, in which the nature of the counterion (I–or OTf–) significantly impacts the structural interactions between Fe and the Co6Se8unit. Experimental characterization by single crystal X-ray diffraction,57Fe Mössbauer spectroscopy, and31P{1H} NMR spectroscopy is complemented by computational analysis. In aggregate, the study reveals that upon oxidation, the charge is shared between the Fe edge site and the Co6Se8core.