Yuan W.Z.,Hong Kong University of Science and Technology |
Yuan W.Z.,Shanghai JiaoTong University |
Hu R.,Hong Kong University of Science and Technology |
Lam J.W.Y.,Hong Kong University of Science and Technology |
And 4 more authors.
Chemistry - A European Journal | Year: 2012
Triphenylamine (TPA)-based conjugated hyperbranched poly(aryleneethynylene) s (PAEs), hb-P1/2, hb-P1/3, and hb-P1/4, were synthesized with high molecular weights and good solubilities through Sonogashira coupling reactions. These PAEs exhibited outstanding thermal stabilities and different emission behaviors. Tetraphenylethene (TPE)-containing hb-P1/2 fluoresced faintly in THF, although its light emission was enhanced by aggregate formation in aqueous media or in thin films, thereby exhibiting an aggregation-induced emission-enhancement (AIEE) effect. Whereas 1,1,2,3,4,5-hexaphenylsilole (HPS)-bearing hb-P1/3 showed no significant change in emission intensity with increasing water content in aqueous media, hb-P1/4, which consisted of TPA-fluorenone donor-acceptor groups, presented almost identical absorptions, but both positive and negative solvatochromic emissions in various solvents. A superquenching effect was observed in the picric-acid-detection process by using nanosuspensions of hb-P1/2. All of the polymers possessed good film formability. UV irradiation of the thin films induced simultaneous photobleaching and cross-linking, thus making them applicable in the fabrication of 2D and 3D patterns. Furthermore, the polymer films also showed high refractive indices, which were tunable upon exposure to UV light. Branching out: Soluble, conjugated hyperbranched poly(aryleneethynylene)s (hb-PAEs) exhibit outstanding thermal stabilities and intriguing photophysical properties, such as aggregation-induced emission enhancement. These hb-PAEs also enjoy excellent film formability, photopatternability, and tunable high refractive indices, which render them promising candidates in optoelectronic applications. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Liu J.,Hong Kong University of Science and Technology |
Liu J.,State Key Laboratory of Molecular Neuroscience HKUST |
Liu J.,Fok Ying Tung Research Institute |
Su H.,HKUST |
And 18 more authors.
Chemical Science | Year: 2012
In this contribution, we conceptually present a new avenue to construction of molecular functional materials with high performance of circularly polarised luminescence (CPL) in the condensed phase. A molecule (1) containing luminogenic silole and chiral sugar moieties was synthesized and thoroughly characterized. In a solution of 1, no circular dichroism (CD) and fluorescence emission are observed, but upon molecular aggregation, both the CD and fluorescence are simultaneously turned on, showing aggregation-induced CD (AICD) and emission (AIE) effects. The AICD effect is supported by the fact that the molecules readily assemble into right-handed helical nanoribbons and superhelical ropes when aggregated. The AIE effect boosts the fluorescence quantum efficiency (Φ F) by 136 fold (Φ F, ∼0.6% in the solution versus ∼81.3% in the solid state), which surmounts the serious limitations of aggregation-caused quenching effect encountered by conventional luminescent materials. Time-resolved fluorescence study and theoretical calculation from first principles conclude that restriction of the low-frequency intramolecular motions is responsible for the AIE effect. The helical assemblies of 1 prefer to emit right-handed circularly polarised light and display large CPL dissymmetry factors (g em), whose absolute values are in the range of 0.08-0.32 and are two orders of magnitude higher than those of commonly reported organic materials. We demonstrate for the first time the use of a Teflon-based microfluidic technique for fabrication of the fluorescent pattern. This shows the highest g em of -0.32 possibly due to the enhanced assembling order in the confined microchannel environment. The CPL performance was preserved after more than half year storage under ambient conditions, revealing the excellent spectral stability. Computational simulation was performed to interpret how the molecules in the aggregates interact with each other at the molecular level. Our designed molecule represents the desired molecular functional material for generating efficient CPL in the solid state, and the current study shows the best results among the reported organic conjugated molecular systems in terms of emission efficiency, dissymmetry factor, and spectral stability. © 2012 The Royal Society of Chemistry.