碗状钒酸盐和Lindqvist型钼钨酸盐衍生物氧化还原及非线性光学性质的理论研究
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摘要
多酸(即多金属氧酸盐,简写成POMs或金属氧簇,Metal-Oxogen Cluster)是一类由d0构型的前过渡金属离子通过氧连接而成的多核配合物,主要的结构单元{MO4}四面体和{MO6}八面体通过共边、共角或共面构筑不同功能和结构多酸阴离子。由于它们的稳定性以及优异的化学、物理和生物特性,被广泛应用于光、电、磁、催化、生物和医药等各个领域。多酸已经进入分子剪裁和组装阶段,对分子材料在分子水平上进行设计,期望合成具有光、电、磁等多种物理性质的多酸复合物,并开始对亚稳态和变价化合物以及超分子化合物进行研究。由于现有的表征手段尚无法满足研究的进一步要求,人们开始借助于量子化学手段在微观水平上探讨其结构和性质之间的关系。计算机技术的发展促使量子化学计算作为一种理论研究方法进入多酸化学领域。早期人们尝试用ab initio Hartree–Fock (HF)方法在研究多金属氧酸盐的结构及电子性质方面取得了一些成果。随着研究的不断深入,多酸及其衍生物的电子性质、氧化还原、催化、光学等性质可以指导和预测实验合成及材料制备,因此备受关注。
本论文采用量子化学计算方法探讨了一系列有机取代四核钒酸盐和Linqvist型多酸衍生物的氧化还原性质及非线性光学性质。研究工作主要包括以下四个方面: 1.采用密度泛函理论对四核内嵌钒氧酸盐体系的极化作用和氧化还原客体开关性质进行研究。结果表明钒酸盐碗状结构可以束缚不同的客体阴离子。主体具有大的极化率,可以将束缚在碗内的客体阴离子极化,并使电子从客体转移到主体碗状结构。不同客体离子的引入可以产生不同的氧化还原电位,这种特性使这种四核钒酸盐的主客体化合物有望成为基于不同客体离子的氧化还原开关。
2.采用DFT方法对不同有机胺取代的Lindqvist型钼酸盐的氧化还原性质和二阶非线性光学响应进行研究。研究发现有机共轭基团的引入较非共轭基团来讲对体系的氧化还原性质和β值影响更大。共轭电子供体基团的数目,也就是有机片段与无机多酸阴离子之间的净供电荷的能力对体系的氧化还原电位影响很大,能够使电位大幅度负移,而相比之下,有机共轭链长的增加可以明显提高体系的二阶非线性光学响应。
3.理论表征了基于多酸片段的可逆氧化还原过渡金属中心的2-D偶极的NLO活性的邻二氮杂菲-多酸化合物。这类化合物沿着y轴的非对角张量βzyy很大,较大的各向异性值证实了它们具有较好的2-D特性。值得注意的是,电子添加到多酸受体的高价金属Mo上使还原态体系的NLO响应得到巨大提高,由于Ni原子的引入使还原态化合物的二阶NLO响应比氧化态化合物的NLO值提高近1019倍。因此,这些化合物的NLO活性可以通过氧化还原活性的杂化邻二氮杂菲-多酸化合物中过渡金属MoVI/V氧化还原电对来进行有效的可逆调控,并且有望成为非线性光学响应的可逆氧化还原开关材料,可以广泛应用在光电子领域上。
4.通过比较含Ti的芳醇取代的杂化单-和双-TiW_5O_(18)衍生物与纯无机多酸化合物的氧化还原性质和电子光谱性质,发现有机共轭芳醇基团的引入削弱了体系的Ti-Oc键,并修饰了HOMO轨道布局,较纯无机的多酸化合物有更活性的氧化还原性质,且Ti原子更趋向于作为活性的氧化还原中心。双-TiW_5O_(18)衍生物比单-TiW_5O_(18)衍生物的能隙更小,氧化还原性质更活泼。有机共轭基团的引入使体系的低能电子跃迁发生明显红移,电子从有机π共轭供体转移到多酸框架中的d-Ti轨道和部分Oc轨道。含Ti的芳醇取代的杂化化合物通过Ti-O-C键提供一种简便的连接方式将多酸化合物嫁接到二氧化硅表面,从而显示比纯无机多酸化合物更好的催化性能。
Polyoxometalates (POMs or metal-oxygen clusters) are a rich family of polynuclear compounds which are made up of early transitional metals with d0 electron configuration linked by oxygen atoms, and their significant units {MO4} and {MO6} can build kinds of polyanions with different function and structure by edge-shared, angle-shared or face-shared approach. POMs has promised dramatic applications in many areas including optics, electrics, magnetics, catalysis, biology and medicine due to their thermostability and novel chemical, physical and biological properties. Recently, the synthesis of POMs has come into the molecular assembling which can be designed at the molecular level to synthesize POM complexes with optical, electrical and magnetical properties. Moreover, the investigation tends to focus on the compounds with metastability and variable valence with supermolecules instead of oxidated species. The futher research has been prohibited due to the present deficient characterization appoarch, so the quantumn chemistry calculation as a theoretical method has been introduced into the field of POMs and investigated the structure-property relationship at the micro-level. In early time, the ab initio Hartree–Fock (HF) approximation presented reasonable achievment for studying the structural and electronic properties of POMs. Moreover, the electronic, redox, catalytic and optical properties of the POM derivatives which can guide synthesis and material preparation have attracted more attention. In this thesis, quantum chemistry calculations have been performed to investigate redox properties and second-order nonlinear optical (NLO) response for a series of organic-inorganic hybrid tetranuclear endohedral vanadate and Lindqvist-type POM derivatives. The present work has been focused on the following four aspects:
1. Density Functional Theory (DFT) calculations were carried out to investigate the polarization and redox-switching properties of tetranuclear endohedral vanadate. It indicated that the bowl-shaped vanadate with large polarizability can attach different guest anions, and polarize them to evoke electron transition originated from the guest to the host bowl. The introduction of different guest anions can generate distinct redox potentials, which enables the host-guest vanadate to be promisng redox-swicthing materials based on various guest anoins.
2. The redox property and second-order NLO response for organoimido derivatives of Lindqvist-type molybdate has been investigated by DFT method. It was indicated that organic conjugated groups were much more sensitive to the redox property and nonlinear optical response than non–conjugated ones. The increment of organic conjugated group, that is the greater net charge donation between organic segment and inorganic polyanion cluster, drove the first reduction potential dramatically negative. In contrast, the lengthening of conjugated chain resulted in remarkable improvement on second-order nonlinear optical response than in reduction potentials.
3. DFT method has been performed to character the family of 2-D dipolar NLO phenanthroline-POMs based on redox-switchable transition metal centers in POM segment. It is therefore apparent that the electron transition in phenanthroline-POMs exhibits largeβzyy tensor along y-axis to confirm better 2-D character with sizable anisotropy values. Interestingly, the addition of electrons into high-valence metal Mo in POM acceptor evokes dramatic enhancement in NLO response for reduction state by contrast with that for corresponding oxidation state, and compound IIared exhibits nearly 1019 times in second-order NLO response as much as compound IIa owing to the addition of the Ni atom. Therefore, the NLO activity of such compounds can be reversibly and effectively switched via the transition metal MoVI/V redox couple in hybrid redox-active phenanthroline-POMs, and these compounds have turned out to be very promising candidates for redox-switching NLO application and novel optoelectronic applications.
本论文采用量子化学计算方法探讨了一系列有机取代四核钒酸盐和Linqvist型多酸衍生物的氧化还原性质及非线性光学性质。研究工作主要包括以下四个方面: 1.采用密度泛函理论对四核内嵌钒氧酸盐体系的极化作用和氧化还原客体开关性质进行研究。结果表明钒酸盐碗状结构可以束缚不同的客体阴离子。主体具有大的极化率,可以将束缚在碗内的客体阴离子极化,并使电子从客体转移到主体碗状结构。不同客体离子的引入可以产生不同的氧化还原电位,这种特性使这种四核钒酸盐的主客体化合物有望成为基于不同客体离子的氧化还原开关。
2.采用DFT方法对不同有机胺取代的Lindqvist型钼酸盐的氧化还原性质和二阶非线性光学响应进行研究。研究发现有机共轭基团的引入较非共轭基团来讲对体系的氧化还原性质和β值影响更大。共轭电子供体基团的数目,也就是有机片段与无机多酸阴离子之间的净供电荷的能力对体系的氧化还原电位影响很大,能够使电位大幅度负移,而相比之下,有机共轭链长的增加可以明显提高体系的二阶非线性光学响应。
3.理论表征了基于多酸片段的可逆氧化还原过渡金属中心的2-D偶极的NLO活性的邻二氮杂菲-多酸化合物。这类化合物沿着y轴的非对角张量βzyy很大,较大的各向异性值证实了它们具有较好的2-D特性。值得注意的是,电子添加到多酸受体的高价金属Mo上使还原态体系的NLO响应得到巨大提高,由于Ni原子的引入使还原态化合物的二阶NLO响应比氧化态化合物的NLO值提高近1019倍。因此,这些化合物的NLO活性可以通过氧化还原活性的杂化邻二氮杂菲-多酸化合物中过渡金属MoVI/V氧化还原电对来进行有效的可逆调控,并且有望成为非线性光学响应的可逆氧化还原开关材料,可以广泛应用在光电子领域上。
4.通过比较含Ti的芳醇取代的杂化单-和双-TiW_5O_(18)衍生物与纯无机多酸化合物的氧化还原性质和电子光谱性质,发现有机共轭芳醇基团的引入削弱了体系的Ti-Oc键,并修饰了HOMO轨道布局,较纯无机的多酸化合物有更活性的氧化还原性质,且Ti原子更趋向于作为活性的氧化还原中心。双-TiW_5O_(18)衍生物比单-TiW_5O_(18)衍生物的能隙更小,氧化还原性质更活泼。有机共轭基团的引入使体系的低能电子跃迁发生明显红移,电子从有机π共轭供体转移到多酸框架中的d-Ti轨道和部分Oc轨道。含Ti的芳醇取代的杂化化合物通过Ti-O-C键提供一种简便的连接方式将多酸化合物嫁接到二氧化硅表面,从而显示比纯无机多酸化合物更好的催化性能。
Polyoxometalates (POMs or metal-oxygen clusters) are a rich family of polynuclear compounds which are made up of early transitional metals with d0 electron configuration linked by oxygen atoms, and their significant units {MO4} and {MO6} can build kinds of polyanions with different function and structure by edge-shared, angle-shared or face-shared approach. POMs has promised dramatic applications in many areas including optics, electrics, magnetics, catalysis, biology and medicine due to their thermostability and novel chemical, physical and biological properties. Recently, the synthesis of POMs has come into the molecular assembling which can be designed at the molecular level to synthesize POM complexes with optical, electrical and magnetical properties. Moreover, the investigation tends to focus on the compounds with metastability and variable valence with supermolecules instead of oxidated species. The futher research has been prohibited due to the present deficient characterization appoarch, so the quantumn chemistry calculation as a theoretical method has been introduced into the field of POMs and investigated the structure-property relationship at the micro-level. In early time, the ab initio Hartree–Fock (HF) approximation presented reasonable achievment for studying the structural and electronic properties of POMs. Moreover, the electronic, redox, catalytic and optical properties of the POM derivatives which can guide synthesis and material preparation have attracted more attention. In this thesis, quantum chemistry calculations have been performed to investigate redox properties and second-order nonlinear optical (NLO) response for a series of organic-inorganic hybrid tetranuclear endohedral vanadate and Lindqvist-type POM derivatives. The present work has been focused on the following four aspects:
1. Density Functional Theory (DFT) calculations were carried out to investigate the polarization and redox-switching properties of tetranuclear endohedral vanadate. It indicated that the bowl-shaped vanadate with large polarizability can attach different guest anions, and polarize them to evoke electron transition originated from the guest to the host bowl. The introduction of different guest anions can generate distinct redox potentials, which enables the host-guest vanadate to be promisng redox-swicthing materials based on various guest anoins.
2. The redox property and second-order NLO response for organoimido derivatives of Lindqvist-type molybdate has been investigated by DFT method. It was indicated that organic conjugated groups were much more sensitive to the redox property and nonlinear optical response than non–conjugated ones. The increment of organic conjugated group, that is the greater net charge donation between organic segment and inorganic polyanion cluster, drove the first reduction potential dramatically negative. In contrast, the lengthening of conjugated chain resulted in remarkable improvement on second-order nonlinear optical response than in reduction potentials.
3. DFT method has been performed to character the family of 2-D dipolar NLO phenanthroline-POMs based on redox-switchable transition metal centers in POM segment. It is therefore apparent that the electron transition in phenanthroline-POMs exhibits largeβzyy tensor along y-axis to confirm better 2-D character with sizable anisotropy values. Interestingly, the addition of electrons into high-valence metal Mo in POM acceptor evokes dramatic enhancement in NLO response for reduction state by contrast with that for corresponding oxidation state, and compound IIared exhibits nearly 1019 times in second-order NLO response as much as compound IIa owing to the addition of the Ni atom. Therefore, the NLO activity of such compounds can be reversibly and effectively switched via the transition metal MoVI/V redox couple in hybrid redox-active phenanthroline-POMs, and these compounds have turned out to be very promising candidates for redox-switching NLO application and novel optoelectronic applications.
引文
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