新型二維多吡咯共軛稠合多核化合物的設計合成及性質(zhì)研究
發(fā)布時間：2018-09-02 06:35
【摘要】：以苯單元為基本單元的二維共軛碳材料具有顯著的電子特性,在納米電子學和能量轉(zhuǎn)換/儲存器件等方面引起了研究者極大的興趣。通過氮摻雜對這些碳材料來進行修飾調(diào)控,可以得到在光電催化領域中具有很大應用價值的新型催化劑。由于四吡咯結(jié)構(gòu)本征共軛含氮、中心金屬離子可調(diào),由四吡咯單元組成的二維共軛分子材料在納米電子學、能量轉(zhuǎn)換/存儲器件和光電催化等領域都具有重要的科技性。卟啉和酞菁是四吡咯類化合物,具有18π電子共軛體系和高度平面的分子構(gòu)型,表現(xiàn)出獨特的光學和電化學性質(zhì),在光合成天線模型、光動力治療等方面,激發(fā)了眾多研究者的興趣。三吡咯化合物是一類卟啉酞菁縮環(huán)類似物,具有14π電子芳香體系和碗狀分子構(gòu)型,近年來在功能染料分子等方面也引起了研究者密切的關(guān)注。其中尤其是亞酞菁表現(xiàn)出不易聚集、缺電子、光學性質(zhì)可調(diào)等獨特的性質(zhì),引起了研究者的密切關(guān)注。將這些不同的多吡咯生色團稠合起來得到的新型二維功能分子材料,由于其稠合生色團之間有效的電子相互作用,其共軛結(jié)構(gòu)不僅得到了有效擴展,還具有迥異于其單體的物化、光學及電化學等性質(zhì),進而在光合天線模型、分子半導體納米器件、近紅外染料和光動力治療材料等方面中都具有廣泛的應用潛能。本論文設計合成了一系列多吡咯稠合多聚物,并對其進行了結(jié)構(gòu)表征。同時,還研究了它們的光學和電化學性質(zhì)。具體內(nèi)容如下:(1)將酞菁和卟啉生色團通過喹喔啉單元稠合得到了異核四吡咯稠合二聚體和三聚體。鋅二聚體配合物的單晶X射線衍射分析顯示了其異核四吡咯雙核化合物的平面結(jié)構(gòu)。電化學分析、理論計算及時間分辨光譜結(jié)果表明,由于四吡咯發(fā)色團之間的強烈相互作用,兩/三四吡咯-稠合的骨架表現(xiàn)為一個完全π共軛體系。此有效擴展的π電子體系增強了卟啉和酞菁單元間的電子相互作用,提高了其躍遷偶極矩,進而使得這一系列化合物的熒光量子產(chǎn)率較高(0.13),激發(fā)態(tài)壽命較長(1.3 ns)。(2)將卟啉和亞酞菁生色團通過喹喔啉單元稠合得到了首例卟啉-亞酞菁稠合二聚體。單晶X射線衍射分析顯示其具有獨特的平面-碗狀分子結(jié)構(gòu)。穩(wěn)態(tài)及瞬態(tài)光譜、電化學及理論計算結(jié)果顯示其HOMO軌道離域在整個分子骨架上,表明基態(tài)下亞酞菁單元和卟啉單元間存在較強的電子相互作用。然而由于喹喔啉環(huán)的吸電子性質(zhì),在LUMO軌道中電子密度集中于喹喔啉單元而非亞酞菁和卟啉單元。結(jié)果表明在此分子體系內(nèi)存在從四吡咯和三吡咯生色團到喹喔啉單元的分子內(nèi)電荷轉(zhuǎn)移。(3)將具有光學活性的聯(lián)萘單元引入到卟啉-酞菁稠合化合物中酞菁生色團的周邊位置,得到了首例具有誘導手性的卟啉-酞菁稠合二聚體和三聚體。電子吸收、MCD、CD光譜及理論計算結(jié)果表明手性信號從聯(lián)萘基團到中心四吡咯稠合生色團的有效轉(zhuǎn)移,證實了四吡咯生色團之間的有效電子相互作用造成了π電子在稠合體系中的有效離域。(4)設計合成得到卟啉酞菁稠合五聚體陣列,并對其進行了光譜表征。此五聚體的馬鞍狀分子構(gòu)型及周邊大體積取代基使得其在CHCl3和正丁醇的溶劑體系中以分子間CH-π作用力及色散力自組裝成三維超分子納米棒狀結(jié)構(gòu)。粉末XRD及選區(qū)電子衍射結(jié)果表明隨著組裝溫度的升高,納米棒內(nèi)分子長程有序度也逐漸升高,并且納米棒顯示出典型的半導體性質(zhì),其電導率也隨著制備溫度的升高而增加。(5)首次合成表征了二異吲哚、三異吲哚、四異吲哚及六異吲哚的線型異吲哚多聚衍生物。變溫核磁譜圖和理論計算結(jié)果揭示了室溫下在三異吲哚、四異吲哚和六異吲哚化合物內(nèi)均存在外異吲哚單元和內(nèi)異吲哚單元間N-H質(zhì)子的互變異構(gòu)體。單晶結(jié)構(gòu)、電子吸收及熒光光譜、電化學性質(zhì)以及理論計算清晰地闡明了這一系列異吲哚多聚衍生物共軛的電子結(jié)構(gòu)。此外,πMayer鍵級計算結(jié)果表明這一系列異吲哚多聚化合物具有兩種共軛區(qū)域,即整個骨架上的離域共軛線和苯環(huán)單元上的的局部共軛環(huán),弱π鍵將它們連接在一起成為一個整體的共軛體系。特別是其π鍵強度與傳統(tǒng)的環(huán)狀異吲哚多聚物的π鍵相當,再加上他們具有確定的可配位單元,表明它們在傳感器和電子器件等不同領域的應用潛力。
[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.
【學位授予單位】：北京科技大學
【學位級別】：博士
【學位授予年份】：2018
【分類號】：O633.5
本文編號：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.
【學位授予單位】：北京科技大學
【學位級別】：博士
【學位授予年份】：2018
【分類號】：O633.5
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