树枝状共轭有机分子的合成、结构与光电性质
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摘要
结构高度有序的功能化树枝状分子作为有机光电材料受到研究者们越来越广泛的关注。相比于传统的有机小分子和高分子光电材料，功能化树枝状分子在有机光电材料方面的应用具有难以比拟的优势。因此，设计和合成具有优良光电性能的功能化树枝状分子是本论文探索研究的总体目标。本论文利用功能化树枝状分子结构的可调控性，特别是树枝单元的易调控性，通过调换不同的树枝单元来获得不同结构类型的树枝状共轭有机分子。在获得目标树枝状共轭有机分子的基础上，首先，对该类树枝状共轭有机分子进行构效关系研究。其次，作为本论文的研究重点，对于含硼类树枝状共轭有机分子，一方面研究该类树枝状共轭有机分子的溶剂化效应；另一方面，通过F-滴定实验，评价含硼类树枝状共轭有机分子作为F-荧光探针的应用价值。主要研究结果如下：
1.本论文设计合成了S3、SC3、N2S、N2SC、 SC3B3和N2SB总计6个新的树枝状共轭有机分子，具体结构如下：
2.实验过程中培养得到了中间体05和化合物SC3的单晶，并测定了其X-ray单晶结构。两个化合物的晶体数据表明三聚茚具有较好的刚性平面和一定的π共轭效应。SC3的晶体数据显示：噻吩环与乙炔基之间的键长为14.17（9）nm，表现出较好的共轭作用，另外，晶体中分子层与层之间的距离为44.95（8）nm，这表明分子间具有一定的π-π堆积作用。
3. S3、SC3、N2S和N2SC的光谱学数据显示，π共轭体系的扩大和强电子供体型树枝单元的引入，将导致体系的能极差减小，在光谱中表现为红移。另外，通过SC3B3和N2SB与其对应的前体化合物SC3和N2S的光谱数据比较，发现二米基硼树枝单元表现出多枝吸收，单枝发射的现象；与此同时，也说明了该类树枝状共轭有机分子中电子推/拉型树枝单元之间存在协同作用。
4. SC3B3和N2SB的在不同极性溶剂中的荧光光谱数据显示，与SC3B3相比，N2SB表现出更强的溶剂化效应，即对环境极性的响应更为灵敏。另外，对SC3B3和N2SB进行F-滴定实验，研究结果表明：在非质子性溶剂中，树枝状共轭有机分子SC3B3属于turn-off型F-荧光探针，而树枝状共轭有机分子N2SB则属于turn-on型F-荧光探针。
总之，本论文对设计合成的以三聚茚为中心核的树枝状共轭有机分子的光电性质与构效关系做了较为系统的比较，为该类分子的构效关系研究提供了一定的参考价值；另外，本论文对设计合成的含硼化合物SC3B3和N2SB的溶剂化效应和作为F离子荧光探针的价值做了评价，结果表明N2SB对环境极性的响应更为灵敏，同时N2SB属于一种性质优良的turn-on型F-荧光探针。
The functionalized dendrimers are extensively applied as organic photoelectric materialsfor its highly ordered structure, therefore more and more researchers pay attention on itrecently. Compared with traditional organic small molecules and polymer optoelectronicmaterials, functionalized dendrimers applied as organic optoelectronic with incomparableadvantages. Therefore, it is the final target to design and synthesize a series of functionalizeddendrimers with excellent photoelectric properties in this paper. For the structure offunctionalized dendrimers can be regulated, especially the dendron can be changed easilyunder control, we obtain different types of dendritic conjugated organic molecules throughreplacing different dendron. On the basis of obtaining the target dendritic conjugated organicmolecules,at the beginning, we compare the relationship between photoelectric properties andstructure of the series of target dendritic conjugated organic molecules. Subsequently, thedendritic conjugated organic molecules with boron are the focus of research in this paper, wefirstly research the solvents effect on this type of dendritic conjugated organic molecules; andsecongdly throuhgh the fluoride titration experiments, we evaluate the value of the dendrimerconjugated organic molecules with boron as the fluoride fluorescent probes. The results ofour study are shown as follows:
1. The dendritic conjugated organic molecules of S3, SC3, N2S, N2SC, SC3B3andN2SB are firstly synthesized in this paper. And their molecular structure are shown asfollows.
2. During the experiment, we cultured the single crystal of05and SC3.And we analyzedthe crystal strcture of05and SC3by X-ray diffraction. The crystal data of05indicates thatthe truxene would have perfect rigid planar stucture and some certain degree of π conjugatedeffect. The crystal data of SC3indicates that the bond length between the thiophene ring andthe ethynyl is14.17(9) nm, implying good conjugation. Additionally, the distance betweenneighboring layer in the crystal is44.95(8) nm, this data demonstrates a certain π-π stackinginteraction.
3. The spectroscopy data of S3, SC3,N2S and N2SC show that the expansion of πconjugated system and introduction of strong electron dendron, will shorten the gap of energy range in π conjugated system, manifestating of redshift in the spectrum. Additionally, thoughcomparing the spectral data of SC3B3and N2SB with their precursor compounds SC3andN2S, we find that the dimesitylboryl dendron shows multi-dendrons absorption and singledendron fluorescent emission; at the same time, we also find that the synergies of theelectronic push/pull types of dendron exist in these series of dendritic conjugated organicmolecules.
4. The spectroscopy data of SC3B3and N2SB in different polar solvents indicate thatsolvents effect of N2SB is more strongly than SC3B3, in the other word, N2SB is moresensitive than SC3B3to response to the polarity of chemical environment. Additionally, theresult of fluoride titration experiments of SC3B3and N2SB shows that in aprotic solvents,SC3B3is “turn-off” type of fluoride fluorescent probe and N2SB is “turn-on” type offluoride fluorescent probe.
In summary, the relationship of photoelectrical properties and structure of targetcompounds are systematic compared in this paper. This study will provide a certain value ofreference to the studies on the relationship of structure and properties of these series ofmolecules. In addition, the solvents effect and the value of fluoride fluorescent probes ofSC3B3and N2SB are evaluated in this paper and the results show that N2SB is moresensitive than SC3B3to response to the polarity of chemical environment, while N2SB is anexcellent “turn-on” type of fluoride fluorescent probe.
1.本论文设计合成了S3、SC3、N2S、N2SC、 SC3B3和N2SB总计6个新的树枝状共轭有机分子，具体结构如下：
2.实验过程中培养得到了中间体05和化合物SC3的单晶，并测定了其X-ray单晶结构。两个化合物的晶体数据表明三聚茚具有较好的刚性平面和一定的π共轭效应。SC3的晶体数据显示：噻吩环与乙炔基之间的键长为14.17（9）nm，表现出较好的共轭作用，另外，晶体中分子层与层之间的距离为44.95（8）nm，这表明分子间具有一定的π-π堆积作用。
3. S3、SC3、N2S和N2SC的光谱学数据显示，π共轭体系的扩大和强电子供体型树枝单元的引入，将导致体系的能极差减小，在光谱中表现为红移。另外，通过SC3B3和N2SB与其对应的前体化合物SC3和N2S的光谱数据比较，发现二米基硼树枝单元表现出多枝吸收，单枝发射的现象；与此同时，也说明了该类树枝状共轭有机分子中电子推/拉型树枝单元之间存在协同作用。
4. SC3B3和N2SB的在不同极性溶剂中的荧光光谱数据显示，与SC3B3相比，N2SB表现出更强的溶剂化效应，即对环境极性的响应更为灵敏。另外，对SC3B3和N2SB进行F-滴定实验，研究结果表明：在非质子性溶剂中，树枝状共轭有机分子SC3B3属于turn-off型F-荧光探针，而树枝状共轭有机分子N2SB则属于turn-on型F-荧光探针。
总之，本论文对设计合成的以三聚茚为中心核的树枝状共轭有机分子的光电性质与构效关系做了较为系统的比较，为该类分子的构效关系研究提供了一定的参考价值；另外，本论文对设计合成的含硼化合物SC3B3和N2SB的溶剂化效应和作为F离子荧光探针的价值做了评价，结果表明N2SB对环境极性的响应更为灵敏，同时N2SB属于一种性质优良的turn-on型F-荧光探针。
The functionalized dendrimers are extensively applied as organic photoelectric materialsfor its highly ordered structure, therefore more and more researchers pay attention on itrecently. Compared with traditional organic small molecules and polymer optoelectronicmaterials, functionalized dendrimers applied as organic optoelectronic with incomparableadvantages. Therefore, it is the final target to design and synthesize a series of functionalizeddendrimers with excellent photoelectric properties in this paper. For the structure offunctionalized dendrimers can be regulated, especially the dendron can be changed easilyunder control, we obtain different types of dendritic conjugated organic molecules throughreplacing different dendron. On the basis of obtaining the target dendritic conjugated organicmolecules,at the beginning, we compare the relationship between photoelectric properties andstructure of the series of target dendritic conjugated organic molecules. Subsequently, thedendritic conjugated organic molecules with boron are the focus of research in this paper, wefirstly research the solvents effect on this type of dendritic conjugated organic molecules; andsecongdly throuhgh the fluoride titration experiments, we evaluate the value of the dendrimerconjugated organic molecules with boron as the fluoride fluorescent probes. The results ofour study are shown as follows:
1. The dendritic conjugated organic molecules of S3, SC3, N2S, N2SC, SC3B3andN2SB are firstly synthesized in this paper. And their molecular structure are shown asfollows.
2. During the experiment, we cultured the single crystal of05and SC3.And we analyzedthe crystal strcture of05and SC3by X-ray diffraction. The crystal data of05indicates thatthe truxene would have perfect rigid planar stucture and some certain degree of π conjugatedeffect. The crystal data of SC3indicates that the bond length between the thiophene ring andthe ethynyl is14.17(9) nm, implying good conjugation. Additionally, the distance betweenneighboring layer in the crystal is44.95(8) nm, this data demonstrates a certain π-π stackinginteraction.
3. The spectroscopy data of S3, SC3,N2S and N2SC show that the expansion of πconjugated system and introduction of strong electron dendron, will shorten the gap of energy range in π conjugated system, manifestating of redshift in the spectrum. Additionally, thoughcomparing the spectral data of SC3B3and N2SB with their precursor compounds SC3andN2S, we find that the dimesitylboryl dendron shows multi-dendrons absorption and singledendron fluorescent emission; at the same time, we also find that the synergies of theelectronic push/pull types of dendron exist in these series of dendritic conjugated organicmolecules.
4. The spectroscopy data of SC3B3and N2SB in different polar solvents indicate thatsolvents effect of N2SB is more strongly than SC3B3, in the other word, N2SB is moresensitive than SC3B3to response to the polarity of chemical environment. Additionally, theresult of fluoride titration experiments of SC3B3and N2SB shows that in aprotic solvents,SC3B3is “turn-off” type of fluoride fluorescent probe and N2SB is “turn-on” type offluoride fluorescent probe.
In summary, the relationship of photoelectrical properties and structure of targetcompounds are systematic compared in this paper. This study will provide a certain value ofreference to the studies on the relationship of structure and properties of these series ofmolecules. In addition, the solvents effect and the value of fluoride fluorescent probes ofSC3B3and N2SB are evaluated in this paper and the results show that N2SB is moresensitive than SC3B3to response to the polarity of chemical environment, while N2SB is anexcellent “turn-on” type of fluoride fluorescent probe.
引文
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