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

doi:10.11944/j.issn.1000-0518.2017.02.160146

Chinese Journal of Applied Chemistry ›› 2017, Vol. 34 ›› Issue (2): 172-179.DOI: 10.11944/j.issn.1000-0518.2017.02.160146

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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^*()

^aState Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China
^bUniversity of Chinese Academy of Science,Beijing 100039,China
^cResearch Center of Nano Materials and Engineering,He'nan University,Kaifeng,He'nan 475004,China

Received:2016-04-11 Accepted:2016-06-08 Published:2017-01-18 Online:2017-01-18
Contact: WANG Hua,CHENG Yanxiang
Supported by:
Supported by the National Natural Science Foundation of China(No.21174141, No.51303172, No.21404101)

Abstract

Abstract:

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.

Key words: aryl palladium complexes, polyfluorene, catalyst-transfer polymerization, dithieno[2,3-b:2',3'-d]thiophene

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.

References

[1]	CHEN Lei,CHENG Yanxiang,XIE Zhiyuan,et al.Red Electroluminescent Polyfluorenes Containing D-A Type Naphothiadiazole and Benzoselenadiazole[J]. Chinese J Appl Chem,2011,28(11):1229-1238(in Chinese). 陈磊,程延祥,谢志元,等. 聚芴主链含D-A型萘并噻二唑和苯并硒二唑衍生物的红光高分子发光材料[J]. 应用化学,2011,28(11):1229-1238.
[2]	LI Zidong,ZHAO Xiaoli,YANG Xiaoniu. Advance on Device Thermal Stability of Polymer Solar Cells[J]. Chinese J Appl Chem,2016,33(1):1-17(in Chinese). 李自东,赵小李,杨小牛. 聚合物太阳能电池器件热稳定性的研究进展[J]. 应用化学,2016,33(1):1-17.
[3]	LI Jing,FU Hongwei,HU Pan,et al.Amphiphatic Palladium Complexes with Polyethoxylated Groups and Their Application in Synthesis of Poly(9,9-dioctyfluorene)[J]. Acta Polym Sin,2013,(9):1143-1150(in Chinese). 李静,付宏伟,胡盼,等. 低聚乙氧基醚链修饰的两亲性钯化合物及催化合成聚芴[J]. 高分子学报,2013,(9):1143-1150.
[4]	BIAN Chunlei,JIANG Guoxin,CHENG Yanxiang,et al.Poly(Aryl Ether)s for Efficient White Electroluminescence with Simultaneous Bicolor Emission[J]. Acta Polym Sin,2012,(3):334-343(in Chinese). 卞春雷,江国新,程延祥,等. 基于聚芳醚的双色白光聚合物的合成与光物理及电致发光性能[J]. 高分子学报,2012,(3):334-343.
[5]	Bernius M T,Inbasekaran M, O'Brien J, et al. Progress with Light-emitting Polymers[J]. Adv Mater,2000,12(23):1737-1750.
[6]	Knappke C E I,Wangelin A J V. 35 Years of Palladium-catalyzed Cross-coupling with Grignard Reagents:How Far Have We Come[J]. Chem Soc Rev,2011,40(40): 4948-4962.
[7]	Amarajothi D,Asiri A M,Hermenegildo G. Metal-Organic Frameworks Catalyzed C-C and C-Heteroatom Coupling Reactions[J]. Chem Soc Rev,2011,44(7):1922-1947.
[8]	Sellars J D,Steel P G. Transition Metal-catalysed Cross-coupling Reactions of P-Activated Enols[J]. Chem Soc Rev,2011,40(10):5170-5180.
[9]	Kappaun S,Scheiber H,Trattnig R,et al.Defect Chemistry of Polyfluorenes:Identification of the Origin of “Interface Defects” in Polyfluorene Based Light-emitting Devices[J]. Chem Commun,2008,41(41):5170-5172.
[10]	Sheina E E,Liu J S,Iovu M C,et al.Chain Growth Mechanism for Regioregular Nickel-initiated Cross-coupling Polymerizations[J]. Macromolecules,2004,37(10):3526-3528.
[11]	Yokoyama A,Miyakoshi R,Yokozawa T. Chain-growth Polymerization for Poly(3-Hexylthiophene) with a Defined Molecular Weight and a Low Polydispersity[J]. Macromolecules,2004,37(4):1169-1171.
[12]	Yokoyama A,Suzuki H,Kubota Y,et al.Chain-growth Polymerization for the Synthesis of Polyfluorene via Suzuki-Miyaura Coupling Reaction from an Externally Added Initiator Unit[J]. J Am Chem Soc,2007,129(23):7236-7237.
[13]	Fischer C S,Baier M C,Mecking S. Enhanced Brightness Emission-tuned Nanoparticles from Heterodifunctional Polyfluorene Building Blocks[J]. J Am Chem Soc,2013,135(3):1148-1154.
[14]	Zhang H H, Hu Q S,Hong K. Accessing Conjugated Polymers with Precisely Controlled Heterobisfunctional Chain Ends via Post-polymerization Modification of the OTf Group and Controlled Pd(0)/t-Bu3P-catalyzed Suzuki Cross-coupling Polymerization[J]. Chem Commun,2015,51(51):14869-14872.
[15]	Elmalem E,Biedermann F,Johnson K,et al.Synthesis and Photophysics of Fully π-Conjugated Heterobis-functionalized Polymeric Molecular Wires via Suzuki Chain-growth Polymerization[J]. J Am Chem Soc,2012,134(42):17769-17777.
[16]	Yokozawa T,Ohta Y. Transformation of Step-growth Polymerization into Living Chain-growth Polymerization[J]. Chem Rev,2016,116(4):1950-1968.
[17]	Fu H W,Li J,Zhang Z L,et al.Synthesis of Novel Polyfluorene with Defined Group in the Center Using Aryl Dipalladium Complex as an Initiator[J]. J Organomet Chem,2013,738(15):55-58.
[18]	Zhang Z L,Hu P,Li X,et al.Investigation of Suzuki Miyaura Catalyst-transfer Polycondensation of AB-Type Fluorene Monomer Using Coordination-saturated Aryl Pd(Ⅱ) Halide Complexes as Initiators[J]. J Polym Sci Polym Chem,2015,53(12):1457-1463.
[19]	Wang Y G,Wang Z H,Zhao D F,et al.Efficient Synthesis of Trimethylsilyl-Substituted Dithieno[2,3-b:3',2'-d]thiophene, Tetra[2,3-thienylene] and Hexa[2,3-thienylene] from Substituted [3,3']Bithiophenyl[J]. Synlett,2007,3(15):2390-2394.
[20]	Sun H L,Shi J W,Zhang Z L,et al.Synthesis and Structure of Bull's Horn-shaped Oligothienoacene with Seven Fused Thiophene Rings[J]. J Org Chem,2013,78(12):6271-6275.
[21]	Wang Z H,Shi J W,Wang J,et al.Syntheses and Crystal Structures of Benzohexathia[7]Helicene and Naphthalene Cored Double Helicene[J]. Org Lett,2010,12(3):456-458.
[22]	Li C L,Shi J W,Xu L,et al.Syntheses and Crystal Structures of Fused Thiophenes:[7]Helicene and Double Helicene, a D2-Symmetric Dimer of 3,3'-Bis(Dithieno[2,3-b:3',2'-d]Thiophene)[J]. J Org Chem,2009,74(1):408-412.
[23]	Yi W J,Zhang S,Sun H L,et al.Isomers of Organic Semiconductors Based on Dithienothiophenes:The Effect of Sulphur Atoms Positions on the Intermolecular Interactions and Field-effect Performances[J]. J Mater Chem C,2015,3(3):10856-10861.
[24]	Shi J W,Li Y B,Jia M,et al.Organic Semiconductors Based on Annelated Boligothiophenes and Its Application for Organic Field-effect Transistors[J]. J Mater Chem,2011,8(44):17612-17614.
[25]	Zhang Z J,Tian H K,Liu Q,et al.Synthesis of Fluorene-based Oligomeric Organoboron Reagents via Kumada, Heck, and Stille Cross-coupling Reactions[J]. J Org Chem,2006,71(11):4332-4335.
[26]	Lin S T,Tung Y C,Chen W C,et al.Synthesis, Structures and Multifunctional Sensory Properties of Poly[2,7-(9,9-Dihexylfluorene)]-block-Poly[2-(Dimethylamino)Ethylmethacrylate] Rod-coil Diblock Copolymers[J]. J Mater Chem,2008,18(33):3985-3992.
[27]	Zhang H H,Xing C H,Hu Q S,et al.Controlled Pd(0)/t-Bu3P-catalyzed Suzuki Cross-coupling Polymerization of AB-type Monomers with PhPd(t-Bu3P)I or Pd2(dba)3/t-Bu3P/ArI as the Initiator[J]. J Am Chem Soc,2012,134(32):13156-13159.
[28]	Yokozawa T,Suzuki R,Nojima M,et al.Precision Synthesis of Poly(3-Hexylthiophene) from Catalyst-transfer Suzuki-Miyaura Coupling Polymerization[J]. Macromol Rapid Commun,2011,32(11):801-806.
[29]	GUO D C,SHENG H Q. Preferential Oxidative Addition in Palladium(0)-catalyzed Suzuki Cross-coupling Reactions of Dihaloarenes with Arylboronic Acids[J]. J Am Chem Soc,2005,36(48):10006-10007.
[30]	Weber S K,Frank G,Ullrich S. Preferential Oxidative Addition in Suzuki Cross-coupling Reactions Across One Fluorene Unit[J]. Org Lett,2006,8(18):4039-4044.

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

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[1]	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): 0-0.
[2]	CHEN Lei1,2, CHENG Yanxiang1, XIE Zhiyuan1, WANG Lixiang1*. Red Electroluminescent Polyfluorenes Containing D-A Type Naphthothiadiazole and Benzoselenadiazole Derivatives in the Main Chain [J]. Chinese Journal of Applied Chemistry, 2011, 28(11): 1229-1238.