新型二维多吡咯共轭稠合多核化合物的设计合成及性质研究
发布时间：2018-09-02 06:35
【摘要】：以苯单元为基本单元的二维共轭碳材料具有显著的电子特性,在纳米电子学和能量转换/储存器件等方面引起了研究者极大的兴趣。通过氮掺杂对这些碳材料来进行修饰调控,可以得到在光电催化领域中具有很大应用价值的新型催化剂。由于四吡咯结构本征共轭含氮、中心金属离子可调,由四吡咯单元组成的二维共轭分子材料在纳米电子学、能量转换/存储器件和光电催化等领域都具有重要的科技性。卟啉和酞菁是四吡咯类化合物,具有18π电子共轭体系和高度平面的分子构型,表现出独特的光学和电化学性质,在光合成天线模型、光动力治疗等方面,激发了众多研究者的兴趣。三吡咯化合物是一类卟啉酞菁缩环类似物,具有14π电子芳香体系和碗状分子构型,近年来在功能染料分子等方面也引起了研究者密切的关注。其中尤其是亚酞菁表现出不易聚集、缺电子、光学性质可调等独特的性质,引起了研究者的密切关注。将这些不同的多吡咯生色团稠合起来得到的新型二维功能分子材料,由于其稠合生色团之间有效的电子相互作用,其共轭结构不仅得到了有效扩展,还具有迥异于其单体的物化、光学及电化学等性质,进而在光合天线模型、分子半导体纳米器件、近红外染料和光动力治疗材料等方面中都具有广泛的应用潜能。本论文设计合成了一系列多吡咯稠合多聚物,并对其进行了结构表征。同时,还研究了它们的光学和电化学性质。具体内容如下:(1)将酞菁和卟啉生色团通过喹喔啉单元稠合得到了异核四吡咯稠合二聚体和三聚体。锌二聚体配合物的单晶X射线衍射分析显示了其异核四吡咯双核化合物的平面结构。电化学分析、理论计算及时间分辨光谱结果表明,由于四吡咯发色团之间的强烈相互作用,两/三四吡咯-稠合的骨架表现为一个完全π共轭体系。此有效扩展的π电子体系增强了卟啉和酞菁单元间的电子相互作用,提高了其跃迁偶极矩,进而使得这一系列化合物的荧光量子产率较高(0.13),激发态寿命较长(1.3 ns)。(2)将卟啉和亚酞菁生色团通过喹喔啉单元稠合得到了首例卟啉-亚酞菁稠合二聚体。单晶X射线衍射分析显示其具有独特的平面-碗状分子结构。稳态及瞬态光谱、电化学及理论计算结果显示其HOMO轨道离域在整个分子骨架上,表明基态下亚酞菁单元和卟啉单元间存在较强的电子相互作用。然而由于喹喔啉环的吸电子性质,在LUMO轨道中电子密度集中于喹喔啉单元而非亚酞菁和卟啉单元。结果表明在此分子体系内存在从四吡咯和三吡咯生色团到喹喔啉单元的分子内电荷转移。(3)将具有光学活性的联萘单元引入到卟啉-酞菁稠合化合物中酞菁生色团的周边位置,得到了首例具有诱导手性的卟啉-酞菁稠合二聚体和三聚体。电子吸收、MCD、CD光谱及理论计算结果表明手性信号从联萘基团到中心四吡咯稠合生色团的有效转移,证实了四吡咯生色团之间的有效电子相互作用造成了π电子在稠合体系中的有效离域。(4)设计合成得到卟啉酞菁稠合五聚体阵列,并对其进行了光谱表征。此五聚体的马鞍状分子构型及周边大体积取代基使得其在CHCl3和正丁醇的溶剂体系中以分子间CH-π作用力及色散力自组装成三维超分子纳米棒状结构。粉末XRD及选区电子衍射结果表明随着组装温度的升高,纳米棒内分子长程有序度也逐渐升高,并且纳米棒显示出典型的半导体性质,其电导率也随着制备温度的升高而增加。(5)首次合成表征了二异吲哚、三异吲哚、四异吲哚及六异吲哚的线型异吲哚多聚衍生物。变温核磁谱图和理论计算结果揭示了室温下在三异吲哚、四异吲哚和六异吲哚化合物内均存在外异吲哚单元和内异吲哚单元间N-H质子的互变异构体。单晶结构、电子吸收及荧光光谱、电化学性质以及理论计算清晰地阐明了这一系列异吲哚多聚衍生物共轭的电子结构。此外,πMayer键级计算结果表明这一系列异吲哚多聚化合物具有两种共轭区域,即整个骨架上的离域共轭线和苯环单元上的的局部共轭环,弱π键将它们连接在一起成为一个整体的共轭体系。特别是其π键强度与传统的环状异吲哚多聚物的π键相当,再加上他们具有确定的可配位单元,表明它们在传感器和电子器件等不同领域的应用潜力。
[Abstract]:Two-dimensional conjugated carbon materials based on benzene units have remarkable electronic properties, which have attracted great interest in nanoelectronics and energy conversion/storage devices. New catalysts with great application value in the field of photoelectrocatalysis can be obtained by modifying and regulating these carbon materials with nitrogen doping. The two-dimensional conjugated molecular materials consisting of four pyrrole units have important scientific and technological properties in the fields of nanoelectronics, energy conversion/memory devices and photocatalysis due to their intrinsic conjugated nitrogen-containing structure and adjustable central metal ions. Tripyrrole compounds are a class of porphyrin phthalocyanine ring analogues with 14pi electronic aromatic systems and bowl-like molecular configurations, which have attracted much attention in recent years in the field of functional dye molecules. Researchers have paid close attention to the unique properties of phthalocyanines, such as non-aggregation, electron-deficiency and adjustable optical properties, which have attracted much attention. Its conjugated structure not only has been effectively extended, but also has physicochemical, optical and electrochemical properties which are quite different from its monomers. Therefore, it has a wide range of potential applications in photosynthetic antenna models, molecular semiconductor nanodevices, near-infrared dyes and photodynamic therapy materials. The main contents are as follows: (1) Heteronuclear tetrapyrylpyrrole fused dimers and trimers were synthesized by fusing phthalocyanine and porphyrin chromophores with quinoxaline units. The single crystal X-ray diffraction analysis of zinc dimer complexes showed heteronuclear tetrapyrylpyrrole dimers. The results of electrochemical analysis, theoretical calculation and time-resolved spectroscopy show that the two/tri-tetrapyrrole-fused skeleton exhibits a completely pion-conjugated system due to the strong interaction between the tetrapyrrole chromophores. The first porphyrin-phthalocyanine fused dimer was obtained by fusing the porphyrin and phthalocyanine chromophores through quinoxaline units. X-ray diffraction analysis of single crystal showed that it had a unique planar-bowl component. Substructure. Steady and transient spectra, electrochemical and theoretical calculations show that the HOMO orbital delocalization occurs on the whole molecular skeleton, indicating a strong electron interaction between the phthalocyanine unit and the porphyrin unit in the ground state. However, due to the electron absorption properties of quinoxaline ring, the electron density in the LUMO orbital is concentrated in the quinoxaline unit rather than in the subunit. Phthalocyanine and porphyrin units. The results show that there is intramolecular charge transfer from tetrapyrrole and tripyrrole chromophores to quinoxaline units in this molecule system. (3) The optically active binaphthalene unit was introduced into the peripheral position of phthalocyanine chromophores in the porphyrin-phthalocyanine fused compound, and the first chiral porphyrin-phthalocyanine fused compound was obtained. Conjugated dimers and trimers. Electron absorption, MCD, CD spectra and theoretical calculations show that chiral signals are effectively transferred from binaphthalene group to central tetrapyrrole fused chromophore, confirming that the effective electron interaction between tetrapyrrole chromophores results in the effective delocalization of pion electrons in the fused system. (4) Porphyrin phthalocyanines were designed and synthesized. Consolidated pentamer arrays were characterized by spectroscopy. The saddle-like molecular configuration and the surrounding large-volume substituents of the pentamer enabled it to self-assemble into three-dimensional supramolecular nanorod-like structures in the solvent systems of CHCl3 and n-butanol by intermolecular CH-pi interaction force and dispersion force. With the increase of loading temperature, the degree of molecular long-range order in the nanorods also increases gradually, and the nanorods exhibit typical semiconductor properties, and their conductivity increases with the increase of preparation temperature. (5) Linear isoindole derivatives characterized by diisoindole, triisoindole, tetraisoindole and hexaisoindole were synthesized for the first time. The results reveal that there are tautomers of N-H protons between exoindoles and endoindoles in triisoindoles, tetraisoindoles and hexaisoindoles at room temperature. The single crystal structure, electron absorption and fluorescence spectra, electrochemical properties and theoretical calculations clearly illustrate the series of isoindole poly-derivatives. In addition, the calculated results of the bond order of pi-Mayer show that the series of isoindole polymers have two conjugated domains, i.e. the off-domain conjugated lines on the whole skeleton and the local conjugated rings on the benzene ring units. The weak PI bonds connect them together into a whole conjugated system, especially the strength of their PI bonds and the traditional ones. The equivalence of the PI bonds of cyclic isoindole polymers and their definite coordination units indicate their potential applications in various fields such as sensors and electronic devices.
【学位授予单位】：北京科技大学
【学位级别】：博士
【学位授予年份】：2018
【分类号】：O633.5
本文编号：2218555
[Abstract]:Two-dimensional conjugated carbon materials based on benzene units have remarkable electronic properties, which have attracted great interest in nanoelectronics and energy conversion/storage devices. New catalysts with great application value in the field of photoelectrocatalysis can be obtained by modifying and regulating these carbon materials with nitrogen doping. The two-dimensional conjugated molecular materials consisting of four pyrrole units have important scientific and technological properties in the fields of nanoelectronics, energy conversion/memory devices and photocatalysis due to their intrinsic conjugated nitrogen-containing structure and adjustable central metal ions. Tripyrrole compounds are a class of porphyrin phthalocyanine ring analogues with 14pi electronic aromatic systems and bowl-like molecular configurations, which have attracted much attention in recent years in the field of functional dye molecules. Researchers have paid close attention to the unique properties of phthalocyanines, such as non-aggregation, electron-deficiency and adjustable optical properties, which have attracted much attention. Its conjugated structure not only has been effectively extended, but also has physicochemical, optical and electrochemical properties which are quite different from its monomers. Therefore, it has a wide range of potential applications in photosynthetic antenna models, molecular semiconductor nanodevices, near-infrared dyes and photodynamic therapy materials. The main contents are as follows: (1) Heteronuclear tetrapyrylpyrrole fused dimers and trimers were synthesized by fusing phthalocyanine and porphyrin chromophores with quinoxaline units. The single crystal X-ray diffraction analysis of zinc dimer complexes showed heteronuclear tetrapyrylpyrrole dimers. The results of electrochemical analysis, theoretical calculation and time-resolved spectroscopy show that the two/tri-tetrapyrrole-fused skeleton exhibits a completely pion-conjugated system due to the strong interaction between the tetrapyrrole chromophores. The first porphyrin-phthalocyanine fused dimer was obtained by fusing the porphyrin and phthalocyanine chromophores through quinoxaline units. X-ray diffraction analysis of single crystal showed that it had a unique planar-bowl component. Substructure. Steady and transient spectra, electrochemical and theoretical calculations show that the HOMO orbital delocalization occurs on the whole molecular skeleton, indicating a strong electron interaction between the phthalocyanine unit and the porphyrin unit in the ground state. However, due to the electron absorption properties of quinoxaline ring, the electron density in the LUMO orbital is concentrated in the quinoxaline unit rather than in the subunit. Phthalocyanine and porphyrin units. The results show that there is intramolecular charge transfer from tetrapyrrole and tripyrrole chromophores to quinoxaline units in this molecule system. (3) The optically active binaphthalene unit was introduced into the peripheral position of phthalocyanine chromophores in the porphyrin-phthalocyanine fused compound, and the first chiral porphyrin-phthalocyanine fused compound was obtained. Conjugated dimers and trimers. Electron absorption, MCD, CD spectra and theoretical calculations show that chiral signals are effectively transferred from binaphthalene group to central tetrapyrrole fused chromophore, confirming that the effective electron interaction between tetrapyrrole chromophores results in the effective delocalization of pion electrons in the fused system. (4) Porphyrin phthalocyanines were designed and synthesized. Consolidated pentamer arrays were characterized by spectroscopy. The saddle-like molecular configuration and the surrounding large-volume substituents of the pentamer enabled it to self-assemble into three-dimensional supramolecular nanorod-like structures in the solvent systems of CHCl3 and n-butanol by intermolecular CH-pi interaction force and dispersion force. With the increase of loading temperature, the degree of molecular long-range order in the nanorods also increases gradually, and the nanorods exhibit typical semiconductor properties, and their conductivity increases with the increase of preparation temperature. (5) Linear isoindole derivatives characterized by diisoindole, triisoindole, tetraisoindole and hexaisoindole were synthesized for the first time. The results reveal that there are tautomers of N-H protons between exoindoles and endoindoles in triisoindoles, tetraisoindoles and hexaisoindoles at room temperature. The single crystal structure, electron absorption and fluorescence spectra, electrochemical properties and theoretical calculations clearly illustrate the series of isoindole poly-derivatives. In addition, the calculated results of the bond order of pi-Mayer show that the series of isoindole polymers have two conjugated domains, i.e. the off-domain conjugated lines on the whole skeleton and the local conjugated rings on the benzene ring units. The weak PI bonds connect them together into a whole conjugated system, especially the strength of their PI bonds and the traditional ones. The equivalence of the PI bonds of cyclic isoindole polymers and their definite coordination units indicate their potential applications in various fields such as sensors and electronic devices.
【学位授予单位】：北京科技大学
【学位级别】：博士
【学位授予年份】：2018
【分类号】：O633.5
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