Influence of Electronic Configurations on the Modulation of Fermi/Orbital Junction Energies for Directional Electron Transport through 3d 1 , 3d 3 , and 3d 5 Metallosurfactants
Influence of Electronic Configurations on the Modulation of Fermi/Orbital Junction Energies for Directional Electron Transport through 3d 1 , 3d 3 , and 3d 5 Metallosurfactants
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电子构型对 3d 1 、3d 3 和 3d 5 金属表面活性剂定向电子传输的费米/轨道结能量调制的影响
DOI：
10.1021/acs.jpcc.2c04840
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Verani, Cláudio N.
中科院分区：
文献类型：
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作者：
Weeraratne, A. D.;Rani, Neha;Amunugama, Samudra;Perera, S. Sameera;Kpogo, Kenneth K.;Mazumder, Shivnath;Verani, Cláudio N.
设计了两种新型金属表面活性剂，分别含有3d1钒基（IV）和3d3铬（III）离子，结合到苯二胺桥接的富酚酸配体ln2o2上，形成单层膜沉积在金电极上，并在Au|LB|Au结中探测定向电子转移。[V = OIVLN2O2](1)和[CrIII(LN2O2)(MeOH)(H2O)]Cl(2)促进电流整流。通过协调一致的实验和计算工作，我们将1和2的行为与我们之前研究的3d5[FeIII(LN2O2)Cl](3)的行为进行了比较。基于综合的电化学、光谱和显微镜结果与DFT计算的分析，我们提出了不同的机制，通过这些机制，电子构型影响电极费米能级和负责电子传输的不同分子轨道之间的能隙。虽然3d5物种3显示电子通过位于电极费米能级以上的金属基SOMO传输，但3d1物种1使用费米能级以下的金属基SOMO，并且3d3物种2利用基于配体的HOMO，当施加偏压时，它变得可用。
Two new metallosurfactants containing the 3d1vanadyl(IV) and 3d3chromium(III) ions bound to the phenylenediamine-bridged phenolate-rich ligand LN2O2were designed, deposited as monolayer films on gold electrodes, and probed for directional electron transfer in Au|LB|Au junctions. Both [V═OIVLN2O2](1)and [CrIII(LN2O2)(MeOH)(H2O)]Cl(2)promote current rectification. Through a concerted experimental and computational effort, we compare the behavior of1and2with that of our previously studied 3d5[FeIII(LN2O2)Cl](3). Based on the analysis of comprehensive electrochemical, spectroscopic, and microscopy results allied to DFT calculations, we propose distinct mechanisms by which electronic configurations influence the energy gap between the electrode Fermi levels and the different molecular orbitals responsible for electron transport. While the 3d5species3shows electron transport through the metal-based SOMO located above the Fermi levels of the electrode, the 3d1species1uses a metal-based SOMO below Fermi, and the 3d3species2takes advantage of a ligand-based HOMO, which becomes available when a bias is applied.