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A novel series of donor-acceptor star-shaped conjugated macroelectrolytes(CMEs),denoted as 4FTs,including anionic carboxylic acid sodium groups(4FNaT),neutral diethanolamine groups(4FNOHT),and cationic ammonium groups(4FNBrT),were designed,synthesized,and explored as an excellent platform to investigate the impact of various polar pendent groups on self-assembly behaviors.