Rongqiao Wang,Shibing Chen,Qiaoru Chen,Hongyu Guo,Fafu Yang
abstract Porphyrin with circularly polarized luminescence (CPL) in aggregated state was seldom presented due to the strong aggregation-caused quenching (ACQ) effect at aggregation. This work designed and synthesized a novel porphyrin derivative ( CPL-P ) with good CPL behaviour in aggregated states based on the strong AIE-FRET effect and good chirality transfer of liquid crystalline porphyrin, which was constructed by using porphyrin unit as core with four AIE cyanostilbene groups bearing peripheral chiral alkyl chains. CPL-P exhibited orderly hexagonal columnar mesophase between 62.5 °C and 113.2 °C. It displayed excellent fluorescence emission at 640–760 nm in aggregated states due to the AIE-FRET effect between cyanostilbene unit and porphyrin moiety. Moreover, CPL-P showed the strong circular dichroism and CPL properties in aggregated states based on the effective chiral transfer of the spiral liquid crystalline self-assembly. The |g lum | value for mesophase attained 6.6 × 10 −3 based on the combining effect of AIE-FRET and chiral transfer. This research supplied a new strategy for transferring typical achiral porphyrin with ACQ effect to luminescent molecule with good CPL behaviour in aggregated state.
Hongyu Guo,Sining Zheng,Shibin Chen,Chenyang Han,Fafu Yang
Porphyrins are good near-infrared fluorescent materials, but the strong self-assembly stacking resulted in the aggregation-caused quenching (ACQ) effect, limiting their emissive performance in aggregated states. In this work, a novel diphenylacrylonitrile–porphyrin derivative with multiple polyglycol chains on the periphery was designed and synthesized as an excellent near-infrared-emissive liquid crystalline material in both solution and aggregated states, which was first observed for porphyrin liquid crystals. It exhibited a high self-assembly ability with the ordered hexagonal columnar mesophase between 70 and 120 °C approximately. The strong AIE-FRET effect was produced based on the overlap of the emission wavelength of diphenylacrylonitrile and the absorption wavelength of the porphyrin, resulting in the excellent near-infrared emission in both solution and aggregated states. The pseudo Stokes shift was as large as 210 nm and the fluorescence quantum yield reached 0.12 in the solid state. Moreover, this porphyrin liquid crystal displayed low biotoxicity and excellent fluorescence bio-imaging ability in living cells, opening a new application prospect for porphyrin liquid crystalline materials.
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