四-(叔丁基)-四氮杂卟啉金属配合物振动光谱-DFT计算研究[设计、开题、综述]

BI YE SHE JI

（20 届）

四-（叔丁基）-四氮杂卟啉金属配合物振动光谱-DFT计算研究

所在学院

专业班级化学工程与工艺

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摘要

卟啉类化合物因涉及众多生命过程得到广泛研究。卟啉的四个中位次甲基被氮杂原子取代形成四氮杂卟啉。四氮杂卟啉衍生物有广泛的技术应用，开展四氮杂卟啉的光谱和量子化学计算研究，有助于深入理解其结构与性能关系，为其在各领域的应用提供理论基础。本论文中，我们采用密度泛函理论计算结合光谱实验研究了四苯并四氮杂卟啉(酞著)质子化产物的基态结构及其电子激发态性质，四叔丁基氮杂金属卟啉化合物的振动光谱，以及金属四氮杂氢化卟啉的基态结构、电荷分布和电子光谱等性质。

本论文测量了四-(叔丁基)-四氮杂卟啉金属配合物(MT(tBu)TAP,M=Cu,Co,Ni,Zn)的拉曼和红外光谱。在B3LYP理论水平上计算了其基态结构摘要和振动光谱，基于计算结果和与普通卟啉进行比较对观察到的拉曼谱带和红外谱带进行了详细的指认。考察了拉曼和红外谱带频率变化与四氮杂卟啉环结构的关系。研究表明:随着环内核尺寸(金属与吡咯氮原子问的距离)的减小，CβCβ′伸缩振动(A g)，CαN m不对称伸缩振动(A g)，以及CαN m对称伸缩振动(B g)的频率线性地增加，其中后两者对环内核尺寸的变化更为敏感。有关结果揭示了四氮杂卟啉的振动光谱与分子结构的联系，为其进一步应用奠定基础。

关键词:四氮杂卟啉；密度函数理论；拉曼光谱；红外光谱；基态结构

Abstract

Porphyries and their derivatives have been extensively studied due to their participation in many biological processes. Tetraazaporphyrin is formed when the four meso-methine groups of normal porphyries are replaced by aza nitrogens. Tetraazaporphyrins have a variety of technical applications. The spectroscopic andquantum chemistry computational studies of tetraazaporphyrins are expected to lead to a better understanding of their structure-property relationship and thus provide theoretical basis for their various applications. In this thesis, by using density functional theory calculations and spectral measurements, we investigated the ground-state structures and properties of protonated tetrabenzotetraazaporphyrin (phthalocyanine), the vibrational spectra of tert-butyl substituted metallo-tetraazaporphyrin (MT(tBu)TAP), as well as the molecular structures and the electronic spectra of hydrogenated tetraazaporphyrins.

In this thesis, we studied the infrared absorption and 514.5nm excited Raman spectra for the metallo-tetra-(tert-butyl)-tetraazaporphyrin (MT(tBu)TAP, M=Cu, Co, Ni, Zn). The ground-state structures and vibrational spectra of MT(tBu)TAPs have been calculated at the B3L YP level of theory. The observed Raman and IR bands have been assigned based on the calculation results and by comparing the normal metalloporphyrins. The relationship between the Raman/IR frequencies and the structures of TAP ring was investigated. The results show that the frequencies of CβCβ′tretch (A g, υ2), asymmetric CαN m stretch (A g, υ19), and symmetric CαN m stretch (B g, υ28) modes increase linearly with the decrease of the core-sizes of TAP ring. The υ28 and υ19 modes are more sensitive with respect to the ring expansion in comparison with the υ2mode. Our results correlate the vibrational spectra of tetraazaporphyrins with their molecular structures and will be useful for their further applications.

Keywords: tetraazaporphyrin ；DFT；Raman ；IR ；ground-state structures