Synthesis, photophysical properties and applications of aggregation-induced emission materials based on cyanostilbene moiety

• Main Author: Dong, Yujie
• Format: Others
• Language: English
• Published: HKBU Institutional Repository 2016
• Subjects: Aggregation (Chemistry);Electrochemical analysis;Photoemission
• Online Access: https://repository.hkbu.edu.hk/etd_oa/313; https://repository.hkbu.edu.hk/cgi/viewcontent.cgi?article=1313&context=etd_oa

The concept of "aggregation-induced emission" (AIE) effect has induced a great deal of attention these days. Now, exploration of new AIE-active molecular system and multiple high technique applications for AIE materials are the two research hotspots. Cyanostilbene, as a classical structural unit in photoelectric functional materials, also exhibited this unique luminescence behavior. The research background was illustrated in Chapter 1, which mainly introduced the development of this subject. In this project, Chapter 2 and Chapter 3 presented two classes of functionalized AIE-active molecules based on cyanostilbene moiety, and their applications were investigated, while Chapter 4 demonstrated a series of donor-acceptor (D-A) molecules with highly emissive unit, and their photophysical properties were studied.;In Chapter 2, four different donor-substituted cyanostilbene-based dipyrrins were synthesized and characterized. The investigation of photophysical properties confirms that these molecules are AIE-active, which should be attributed to the cyanostilbene moiety. The introduction of different donor groups showed little impact on their luminescence. Furthermore, the emission properties of these molecules were found to be sensitive to Zn2+, that is, addition of Zn2+ enormously enhanced its fluorescence in THF. The titration experiments proved they showed good selectivity and sensitivity for Zn2+ detection with relatively low limit of detection. Job's curve and spectral studies of their corresponding zinc complex indicated that the ratio for dipyrrins and Zn2+ is 2:1, which suggested the formation of zinc complex by chelation-enhanced fluorescence (CHEF) effect should be the reason of the enhanced fluorescence. By combining dipyrrin with typical AIE-active moiety tetraphenylethylene (TPE), an AIE-active TPE-based dipyrrin was prepared. The studies of its fluorogenic Zn2+ detection confirmed that the CHEF effect together with AIE effect are responsible for the intense fluorescence, indicating the potential application as a Zn2+ detector in aqueous media.;In Chapter 3, the cyanostilbene backbone was functionalized with a terpyridine unit to construct four terpyridine-based cyanostilbene molecules with different donor substitutents. The investigation of their photophysical properties confirms that they are AIEE-active. With the effect of different electron-donating groups, their solid-state fluorescence color was adjusted from blue to orange-red successfully. According to the calculation results of their frontier molecular orbitals, terpyridine has little impacts on their luminescence, but would influence their solid-state emission obviously owing to its large steric hindrance. This class of molecules displayed higher luminescence efficiency in solid state than in their dissolved state. The twisted molecular conformation in single crystal, which effectively avoids close π-π stacking, was assumed to be responsible for the high luminescence efficiency in solid state. This kind of molecules show distinct switched fluorescence by stimuli of acid/base vapors, and this phenomenon derives from the protonation effect of nitrogen atoms in the terpyridine unit. Moreover, three of these molecules exhibit good electroluminescence properties. Especially, the crystal of non-donor substituted molecule show amplified spontaneous emission (ASE) properties, indicating this blue-emissive material can be used in multiple areas such as chemical sensor, organic light emitting diodes (OLEDs) and organic laser media.