Synthesis, characterization and application studies of cyanostilbene-based molecular materials with aggregation-induced emission (AIE) characteristics

  • Wai Sum Lau

Student thesis: Doctoral Thesis


The molecular design, synthesis, spectroscopic and photophysical characterization of a series of cyanostilbene-based compounds are studied in this thesis. The thermal, electrochemical and aggregation induced emission (AIE) properties of these cyanostilbene-based compounds, as well as their application in organic lighting-emitting diodes, live cell imaging, chemical vapor sensor were investigated. Chapter 1 gives a brief introduction on the aggregation-caused quenching (ACQ) behavior of the conventional organic luminogens and the discovery and proposed mechanism of AIE phenomenon. Furthermore, some examples and the applications of these AIE compounds will be discussed. In Chapter 2, triphenylamine- and carbazole-containing cyanostilbene-based derivatives are presented. From the examination of the emission profile, they are all AIE-active through comparison of the photoluminescence intensity in dissolved and in aggregated states. Additionally, the calculation of the enhancement ratio (I/I0 – 1) of each fluorophore was performed in order to quantify its AIE effect. One of our cyanostilbene-based luminogens has achieved an enhancement ratio with a value of 1128. This cyanostilbene-based luminogens has also shown good performance in OLED investigation. In addition to the OLEDs application, the selected cyanostilbene-based luminogens with solid-state emission, cell-permeability and reversible switch-on/off capability have illustrated the positive result in live-cell imaging and chemical vapor sensing. Conjugated polymer with high molecular weight is the superior option by overcoming the weaknesses of low-molecular-weight luminogens with excellent thin-film form ability and comparatively simple and inexpensive fabrication processes. The design and synthesis of the cyanostilbene-based polymeric chromophores are described in Chapter 3. The polymerization of the AIE-active diacetylene ligands by connection of trans-[Pt(PBu3)2] unit at both ends has successfully retained their AIE behavior. In contrast, the ACQ problem has occurred on the polymers with organic spacers and the AIE-active ligands. From the DFT calculation on the Pt polymers and the blue shift of emission spectra in high water content suggested that the AIE phenomenon of Pt polymers is probably originated from the elimination of the non-radiative intramolecular charge transfer (ICT) process. Owing to the high demand in red-emitting materials in the applications of electroluminescent devices, fluorescent sensing and bio-imaging, effort has been made to design a system with the new chromophores with donor (D) – acceptor (A) system and thus to synthesize phenothiazine (D)-containing cyanostilbene (A)-based derivatives which are depicted in Chapter 4. Consistent with the conventional AIE-active luminogens with a successively climb of photoluminescence intensities in response to the increase of water proportion, phenothiazine-containing cyanostilbene-based derivatives has exhibited a V-shape fashion of emission intensity. It suggests that the emission of chromophores started to be quenched due to the increase of solvent polarity, overriding that of the molecular aggregation when a “small” volume of water is being introduced. While aggregate formation was dominant from the addition of a “large” amount of poor solvent, less polar local environment was created which suppressed the non-radiative transition to the ICT state and intensified the emission efficiency. Phenothiazine (D) – cyanostilbene (A) system has created a series of red-emitting chromophores with great tunability for the sake of achieving the desired emission color and better emission efficiency. To functionalize these AIE-active cyanostilbene-based chromophores, pyridine group was attached to the compounds to take the advantage of its metal-chelating capability, which is discussed in Chapter 5. The AIE features of cyanostilbene-based compounds can be preserved after the introduction of the pyridyl unit. Even it possessed a weak photoluminescence in its dilute solution which suggest that the high electron delocalization within the molecule has rigidified the structure to some extent, it is transformed to a highly emissive state with a high proportion of water. The exclusive variation of emission behavior with obvious bathochromic shift and boost of emission spectrum in the presence of cadmium-(II) ion has demonstrated its potential metal ion sensing ability. Chapter 6 and 7 present the concluding remarks and the experimental data of the compounds of Chapter 2 to 5, respectively.
Date of Award25 Aug 2014
Original languageEnglish
SupervisorWai Yeung WONG (Supervisor)

User-Defined Keywords

  • Electrochemical analysis
  • Light emitting diodes
  • Molecules
  • Organic thin films
  • Physical optics

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