Excellent Control of Perylene Diimide End Group in Polyfluorene via Suzuki Catalyst Transfer Polymerization

ix aryl Pd(II) bromide complexes based on perylene diimide derivative (Ar) and phosphine mixed-ligands are successfully synthesized by directly oxidative addition of Ar–Br to the Pd(0) precursor. These complexes with the general formulas ArPdBr(PCy3)2 (PCy3 = tricyclohexylphosphine; Pd1–Pd3) and [ArPdBr(TXP-2,4)]2 (TXP-2,4 = tri-2,4-xylylphosphine; Pd4–Pd6) are stable and can be handled in air at room temperature. By employing the Pd(II) complexes as initiators, Suzuki catalyst transfer polymerization (SCTP) of AB-type fluorene monomer is investigated for preparing polyfluorenes (PFs) with the defined end group. Complexes Pd4–Pd6 with auxiliary TXP-2,4 ligand can initiate polymerization of AB-type fluorene monomer at room temperature, while higher polymerization temperature is required for Pd1–Pd3 with alkyl phosphine PCy3. The obtained polymers are analyzed by matrix-assisted laser desorption ionization-time-of-flight mass spectrometry, which confirms that the Ar group is appended to the terminus of the polymer chain. Moreover, PFs prepared by Pd4–Pd6-catalyzed SCTP bear precisely the Ar group on one chain end and 4-tert-butylphenyl end-capping group on the opposite end, which indicates that Pd4–Pd6 with the bulky TXP-2,4 exhibit better catalytic performance in SCTP. Photoluminescence spectra of the obtained polymers show a dual or a blue emission resulting from the difference of the molecular weight.