Electronic Properties of π-Conjugated Nickel Bis(dithiolene) Network and Its Addition Reactivity with Ethylene
Electronic Properties of π-Conjugated Nickel Bis(dithiolene) Network and Its Addition Reactivity with Ethylene
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DOI：
10.1021/jp405055f
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发表时间：
2013-07
影响因子：
3.7
通讯作者：
Qing Tang;Zhen Zhou
中科院分区：
文献类型：
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作者：
Qing Tang;Zhen Zhou
通过密度泛函理论计算，研究了新制备的二维双（二噻吩）单层镍片的结构、电子性质及其与乙烯的环加成活性。所述镍双（二噻吩）单层具有平面和多孔网络，并在电上作为间接带隙半导体。它的最低未占据态主要分布在S原子的p轨道上，这使得S原子能够从乙烯中C = C键的已占据p轨道上接受电子。我们的计算确实证实了这一点，并且在能量上有利于形成活化能约为21千卡/摩尔的顺式配体间S，S ' -加合物。当添加一个额外的电子时，加成产物变得不稳定，并将解离成乙烯和镍二（二噻吩）阴离子。因此，在可控的条件下，镍双（二噻吩）单层可以在中性和还原条件下结合和释放乙烯分子。
Density functional theory computations were performed to study the structure and electronic properties of the recently achieved two-dimensional nickel bis(dithiolene) single-layer sheet, as well as its cycloaddition activity with ethylene. The nickel bis(dithiolene) monolayer has a planar and porous network, and electrically acts as an indirect band gap semiconductor. Its lowest unoccupied state mainly distributes onto p orbitals of S atoms, which makes S atoms active to accept electrons from the occupied p orbitals of C═C bonds in ethylene. This is indeed confirmed by our computations, and the formation of the cis-interligand S,S′-adduct with an activation energy barrier of about 21 kcal/mol is energetically favored. When an extra electron is added, the addition product becomes destabilized and would dissociate into ethylene and nickel bis(dithiolene) anion. Therefore, with a controllable manner, the nickel bis(dithiolene) monolayer can bind and release ethylene molecules in neutral and reduction conditi...