4.7 Article

Cationic Conjugated Polyelectrolytes with Aggregation-Induced Ratiometric Fluorescence

Journal

MACROMOLECULAR RAPID COMMUNICATIONS
Volume 43, Issue 18, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/marc.202100899

Keywords

aggregation-induced emission; cationic conjugated polyelectrolytes; geminal cross-coupling; ratiometric fluorescence; tetraarylethylene

Funding

  1. National Basic Research Program (973) of China [2015CB755602, 2013CB922104]
  2. National Natural Science Foundation of China [51603078, 21474034, 51673077]
  3. Fundamental Research Funds for the Central Universities [HUST: 2016YXMS029, HUST: 2018KFYXKJC033]
  4. Nature Science Foundation of Hubei Province [2018CFB574]

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In this study, a series of novel polymers were synthesized via geminal cross-coupling, incorporating tetraarylethylene segments into the conjugated backbones. These polymers exhibited pronounced aggregation-induced ratiometric fluorescence and aggregations-caused quenching, with a significant dual emission wavelength difference caused by environmental changes, making them suitable for ratiometric fluorescence sensing.
The molecular diversity of aggregation-induced emission remains a challenge due to the limitation of conventional synthesis methods. Here, a series of novel neutral and cationic conjugated polymers composed of various ratios of tetraarylethylene (TAE) containing a bridged oxygen (O) and fluorene (F) units is designed and synthesized via the geminal cross-coupling (GCC) of 1,1-dibromoolefins. The incorporation of TAE segments into the conjugated backbone of polyfluorene produces pronounced aggregation-induced ratiometric fluorescence, i.e., aggregation-induced emission (AIE) at 520-600 nm and grows synergistically with aggregations-caused quenching (ACQ) at 400-450 nm. The content of fluorene unit in the polymer backbones determines the intensity of the initial fluorescence in the blue light region. The huge distinction (about 150 nm) in dual emission wavelengths caused by the environment change makes these conjugated polyelectrolytes particularly suitable for ratiometric fluorescence sensing. Based on electrostatic interaction mechanism, the gradual addition of heparin into the cationic conjugated polymers aqueous solutions can induce dual-color fluorescence changes with a detection limit of 9 x 10(-9) m. This work exhibits the great facility of using GCC reaction to synthesis the conjugated TAE polymers with superior AIE properties and special functions.

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