Triangular Expanded Hemiporphyrazines: Electronic Structures and Nanoscale Characterization of Their Adlayers on Au(111)
Triangular Expanded Hemiporphyrazines: Electronic Structures and Nanoscale Characterization of Their Adlayers on Au(111)
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DOI：
10.1246/bcsj.20200188
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发表时间：
2021-01-01
影响因子：
4
通讯作者：
Kobayashi, Nagao
中科院分区：
文献类型：
--
作者：
Bacilla, Ana C. C.;Okada, Yusuke;Kobayashi, Nagao
报道了三角形膨胀半紫菜嗪的电子结构和对 Au(111) 吸附层的直接观察，该半紫菜嗪可分类为氮杂卟啉类化合物，可捕获三种过渡金属离子。通过电子吸收和磁圆二色性（MCD）光谱检查电子结构，并结合分子轨道（MO）计算进行解释。无金属化合物和金属化化合物都是 30 π 电子系统，n = 7，芳香性为 4n + 2。此外，还进行了感应电流密度（ACID）和核无关化学位移（NICS）的各向异性的计算。无金属化合物的内核区域具有弱反芳香性或非芳香性，但插入金属后，该区域增加了芳香性。通过扫描隧道显微镜 (STM) 对 Au(111) 上其中一种钴和镍配合物的吸附层进行直接观察表明，这三种离子特别以三角形排列。
Electronic structures and direct observation of adlayers on Au(111) of triangular expanded hemiporphyrazines that can be classified into azaporphyrinoids and which can trap three transition metal ions are reported. The electronic structure was examined by electronic absorption and magnetic circular dichroism (MCD) spectroscopies and interpreted in conjunction with molecular orbital (MO) calculations. Both metal-free and metallated compounds were 30 pi-electron systems with n = 7 in 4n + 2 aromaticity. In addition, calculations of the anisotropy of the induced current density (ACID) and nucleus-independent chemical shift (NICS) were performed. The inner core region of the metal-free compound was weakly antiaromatic or nonaromatic, but after metal insertion, this region increased aromatic character. The direct observation of adlayers of one of their cobalt and nickel complexes on Au(111) by scanning tunneling microscopy (STM) revealed that these three ions are arranged specifically in the shape of a triangle.