Citation: SUN Huiliang, YANG Yike, LI Xiao, WANG Hua, ZHAN Hongmei, CHENG Yanxiang. Polymerization of AB-Type Fluorene Monomer Using Pd (Ⅱ) Complexes Based on Dithieno[2, 3-b: 2', 3'-d]thiophene as Initiators[J]. Chinese Journal of Applied Chemistry, ;2017, 34(2): 172-179. doi: 10.11944/j.issn.1000-0518.2017.02.160146 shu

Polymerization of AB-Type Fluorene Monomer Using Pd (Ⅱ) Complexes Based on Dithieno[2, 3-b: 2', 3'-d]thiophene as Initiators

SUN Huiliang ^a,b ,
YANG Yike ^a,b ,
LI Xiao ^a ,
WANG Hua ^c,*,, ,
ZHAN Hongmei ^a ,
CHENG Yanxiang ^a,*,,

a.
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b.
University of Chinese Academy of Science, Beijing 100039, China
c.
Research Center of Nano Materials and Engineering, He'nan University, Kaifeng, He'nan 475004, China

Corresponding author: WANG Hua, hwang@henu.edu.cn; hwang@henu.edu.cn CHENG Yanxiang, yanxiang@ciac.ac.cn; yanxiang@ciac.ac.cn
Received Date: 11 April 2016
Revised Date: 7 June 2016
Accepted Date: 8 June 2016

Fund Project: the National Natural Science Foundation of China 21404101the National Natural Science Foundation of China 21174141the National Natural Science Foundation of China 51303172

Figures(7)

Aryl palladium complex (bt-DTT) Pd (PCy₃)₂Br was synthesized by oxidative addition of 5-bromo-2-trimethylsilanyl-dithieno[2, 3-b:2', 3'-d]thiophene (bt-DTT-Br) to bis (tericlohexylphosphine) palladium (Pd (PCy₃)₂). X-ray crystal structure analysis reveals that the complex adopts a nearly square-planar geometry around central Pd atom with the expected trans configuration of the phosphine ligands. The complex can initiate the polymerization of AB-type fluorene monomer under heating conditions to afford the polyfluorene with the defined end group of aryl group bt-DTT derived from the complex (bt-DTT) Pd (PCy₃)₂Br. The similar conjugated polymers can also be prepared by employing the aryl palladium complexes in situ generated from bt-DTT-Br/Pd (0)-species as initiators. Polymerization of AB-type fluorene monomers is achieved at room temperature to give the single polyfluorene with the well-defined end groups while initiators are the complexes with the ancillary ligand of tris(2-methylphenyl) phosphine (P (o-tol)₃) or tri-tert-butylphosphine (P (t-Bu)₃). Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectra confirm that the polymers bear a bt-DTT group at one end and a Br/H atom or end-capping group at the other end. Gel permeation chromatography (GPC) analyses demonstrate that molecular mass of polymers increases linearly with increase of the molar ratio of monomer to catalyst, indicating that the polymerizations proceed through the catalyst-transfer mechanism.
- aryl palladium complexes,
- polyfluorene,
- catalyst-transfer polymerization,
- dithieno[2, 3-b:2', 3'-d]thiophene
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