分子内氢键和卤键扩展卟啉pi-共轭体系的研究

Porphyrin containing the stable 4n + 2 pi-electron conjugated plane system has a good thermal and chemical stability and excellent optoelectronic properties for the wide applications including optoelectronic materials and devices, chemical probes, and cell imaging. These optoelectronic properties are affected by the influence of the pi-conjugated system of the porphyrin molecules. In general, the extended pi-conjugated system would lead to increasing the intensity and width of the UV/Visiable absorption, red shifting the absorption and emission spectra, and enlarging the pi-pi overlap and the mobility of charge carriers. To date, the research work on extending pi-conjugated system of porphyrin molecules for the purpose of improving their optoelectronic properties mainly focuses on the introduction of benzene ring or alkynes to the beta- or meso-positions of porphyrin molecules. In this research proposal, we plan to extend the pi-conjugated system of porphyrin molecules by a novel way of intramolecular hydrogen bonding or halogen bonding. A new series of pi-extended porphyrin compounds will be designed and synthesized, and then the effects of intramolecular hydrogen bonding or halogen bonding on their optoelectronic properties as well as their applications in optoelectronic devices, chemical probes, and cell imaging will be investigated.

卟啉环拥有稳定的4n + 2 pi-电子共轭平面体系，具有良好的热、化学稳定性和优良的光电特性，被广泛应用于光电材料及器件、化学探针、细胞成像等领域。这些光电性质都受到卟啉分子的pi-共轭体系的影响，通常较大的pi-共轭体系可以增大其对紫外/可见光的吸收强度和宽度，红移其紫外/可见光吸收和发射光谱，增大pi-pi重叠从而提高载流子的迁移率。目前的国内外研究工作和报道主要从在卟啉环的beta-位或meso-位引入并苯环、炔烃等来扩展卟啉分子的pi-共轭体系，达到改善其光电性质的目的，而本项目拟利用分子内氢键或卤键来扩展卟啉分子的pi-共轭体系，设计、合成出一系列新的卟啉化合物，并研究分子内氢键或卤键对其光电性质的影响及其在光电器件、化学探针、细胞成像等方面。

卟啉环拥有稳定的4n + 2 pi-电子共轭平面体系，具有良好的热、化学稳定性和优良的光电特性，被广泛应用于光电材料及器件、化学探针、细胞成像等领域。这些光电性质都受到卟啉分子的pi-共轭体系的影响，通常较大的pi-共轭体系可以增大其对紫外/可见光的吸收强度和宽度，红移其紫外/可见光吸收和发射光谱，增大pi-pi重叠从而提高载流子的迁移率。目前的国内外研究工作和报道主要从在卟啉环的beta-位或meso-位引入并苯环、炔烃等来扩展卟啉分子的pi-共轭体系，达到改善其光电性质的目的，而本项目拟利用分子内氢键或卤键来扩展卟啉分子的pi-共轭体系，设计、合成出一系列新的卟啉化合物，并研究分子内氢键或卤键对其光电性质的影响及其在光电器件、化学探针、细胞成像等方面。在本项目的支持下，项目主持人作为通讯作者发表12篇文章（Chem. Commun., 2013, 49, 11791-11793；Inorg. Chem., 2014, 53, 3210-3219；J. Mater. Chem. C, 2015, 3, 11099-11110；Analyst, 2015, 140, 7082-7115；New J. Chem., 2015, 39, 492-500；Eur. J. Inorg. Chem., 2016, 4862-4866；Inorg. Chem., 2016, 55, 9221-9229；J. Chem. Educ., 2016, 93, 345-350；Res. Chem. Intermed., 2016, 42, 5027-5048；Mater. Chem. Front., 2017, 1, 1041-1050；RSC Adv., 2017, 7, 7753-7757；RSC Adv., 2017, 7, 40640-40649）和申请中国发明专利一项（专利号: ZL 201210411061.8）。最后，我们对以往的科研工作做了一些深入的总结，发表了一篇综述文章（Analyst, 2015, 140, 7082-7115）。