Tuning the Electronic Structure of Atomically Precise Sn/Co/Se Nanoclusters via Redox Matching of Tin(IV) Surface Sites
Tuning the Electronic Structure of Atomically Precise Sn/Co/Se Nanoclusters via Redox Matching of Tin(IV) Surface Sites
复制标题
DOI：
10.1021/acs.inorgchem.1c00313
复制
发表时间：
2021-04-11
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.;Kaminsky, Werner;Velian, Alexandra
报道了一种新的策略，通过将团簇核心与表面TiN(IV)位进行氧化还原匹配来定制超原子金属硫化物团簇的电子性质。以六价盐[Li-2(Py)(2)](3)Co6Se8L6和R2SnCl2为原料，通过盐析合法合成了两个三元簇合物(SnR2)(3)Co6Se8L6(R=Me，Bu-n)。循环伏安和差分脉冲伏安研究表明，三锡基团簇在Co6Se8核的最高占据轨道-最低未占据分子轨道间隙内具有两个新的近简并电子态，这归因于表面TiN位的还原。单晶X-射线衍射分析表明，固相中不存在锡中心点Se配位。报道了四氢呋喃(THF)加合物变体[Li-2(THF)(2)](6)Co6Se8L6的六硫代盐起始原料的单晶X射线结构。
A new strategy is reported to tailor the electronic properties of a superatomic metal chalcogenide cluster by redox matching the cluster core with surface tin(IV) sites. Two ternary clusters (SnR2)(3)Co6Se8L6 (R = Me, Bu-n) are synthesized by salt metathesis from the hexalithiated salt [Li-2(py)(2)](3)Co6Se8L6 and R2SnCl2. Cyclic and differential-pulse voltammetry studies reveal that the tristannylated clusters feature two new, near-degenerate, electronic states within the highest occupied molecular orbital-lowest unoccupied molecular orbital gap of the Co6Se8 core, which are attributed to the reduction of a surface tin site. Single-crystal X-ray diffraction analysis reveals that no Sn center dot center dot center dot Se coordination is present in the solid state. The single-crystal X-ray structure of the hexalithiated salt starting material is reported for the tetrahydrofuran (THF) adduct variant [Li-2(THF)(2)](6)Co6Se8L6.