958261-50-2 (聚[[9-(1-辛基壬基)-9H-咔唑-2,7-二基]-2,5-噻吩二基-2,1,3-苯并噻二唑-4,7-二基-2,5-噻吩二基],Poly[N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole))

反应条件：

1.1R:R:Cs2CO3, C:PdCl2(PPh3)2, C:4731-65-1, S:p-Cymene, 24 h, 110°C

参考文献：

p-Cymene: A Sustainable Solvent that is Highly Compatible with Direct Arylation Polymerization (DArP)

By Ye, Liwei and Thompson, Barry C., ACS Macro Letters, 2021, 10(6), 714-719

合成路线：5 步

反应条件：

1.1R:SOCl2, S:C5H5N, 0°C; 24 h, reflux
2.1R:Br2, R:HBr, rt → reflux; 2.5 h, reflux
3.1R:K2CO3, C:Pd(PPh3)4, S:(CH2OMe)2, 24 h, 90°C
4.1R:Bromosuccinimide, S:CHCl3, S:AcOH, 6 h, rt
5.1R:Et4N+ OH-, R:(o-MeC6H4)3P, C:Pd2(dba)3, S:H2O, S:PhMe, 72 h, 92°C
5.21 h, 92°C
5.3overnight, reflux

参考文献：

Molecular design and synthesis of low-bandgap polymers containing furan in the main chain

By Wang, Yanbin et al, Changzhou Daxue Xuebao, 2016, 28(4), 36-42

合成路线：1 步

165190-76-1

955964-73-5

反应条件：

1.1

参考文献：

To branch or not to branch: C-H selectivity of thiophene-based donor-acceptor-donor monomers in direct arylation polycondensation exemplified by PCDTBT

By Lombeck, Florian et al, Polymer Chemistry, 2017, 8(32), 4738-4745

合成路线：1 步

反应条件：

1.1

参考文献：

Local Chain Alignment via Nematic Ordering Reduces Chain Entanglement in Conjugated Polymers

By Xie, Renxuan et al, Macromolecules (Washington, 2018, 51(24), 10271-10284

合成路线：3 步

反应条件：

1.1R:BuLi, S:THF, -78°C
1.2
2.1C:Pd2(dba)3, C:(o-MeC6H4)3P
3.1R:R:K2CO3, C:Pd(OAc)2, S:AcNMe2, 48 h, 80°C

参考文献：

Carbazole-based copolymers via direct arylation polymerization (DArP) for Suzuki-convergent polymer solar cell performance

By Gobalasingham, Nemal S. et al, Polymer Chemistry, 2017, 8(30), 4393-4402

合成路线：1 步

_76%

反应条件：

1.1R:K2CO3, S:H2O, S:THF, 10 min, rt
1.2C:Pd(PPh3)4, 24 h, 80-85°C

参考文献：

Random multiacceptor poly(2,7-carbazole) derivatives containing the pentacyclic lactam acceptor unit TPTI for bulk heterojunction solar cells

By Ekiz, Seyma and Thompson, Barry C., Journal of Polymer Science, 2017, 55(17), 2781-2786

合成路线：1 步

反应条件：

1.1R:Et4N+ OH-, C:(o-MeC6H4)3P, C:Pd2(dba)3, S:H2O, S:PhMe, rt → 95°C; 3 h, 95°C
1.2R:PhBr, 1 h, 95°C
1.3R:PhB(OH)2, S:PhMe, 1 h, 95°C

参考文献：

Photoactive Donor-Acceptor Composite Nanoparticles Dispersed in Water

By Parrenin, Laurie et al, Langmuir, 2017, 33(6), 1507-1515

合成路线：6 步

反应条件：

1.1R:NaOMe, S:EtOH, 2 h, reflux
2.1R:Mg, S:Et2O, rt; 16 h, rt; 3 h, reflux
2.2C:(dppp)NiCl2, cooled; 3 d, reflux
2.3R:HCl, S:H2O
3.1R:BBr3, S:CH2Cl2, rt; 1.5 h, reflux
3.2R:NH4Cl, S:H2O
4.1R:Bromosuccinimide, S:THF, S:AcOH, 24 h, rt
4.2S:H2O, rt
5.1R:NaN3, S:DMSO, 10 min, rt; 2 h, rt
5.2S:H2O, rt
6.1R:K3PO4, C:Pd2(dba)3, C:(o-MeC6H4)3P, S:PhMe, 2 h, 120°C
6.2R:30 min, 120°C; 120°C → rt
6.3R:PhBr, 1 h, rt → 120°C
6.4R:EDTA, R:15 min, rt
6.5S:H2O, 1 h, rt

参考文献：

Azido-Functionalized Thiophene as a Versatile Building Block To Cross-Link Low-Bandgap Polymers

By Mueller, Christian J. et al, Macromolecules (Washington, 2016, 49(10), 3749-3760

合成路线：1 步

反应条件：

1.1R:R:t-BuOK, C:Pd(PPh3)4, S:PrOH, 1.5 h, reflux

参考文献：

Low Bandgap Semiconducting Copolymer Nanoparticles by Suzuki Cross-Coupling Polymerization in Alcoholic Dispersed Media

By Parrenin, Laurie et al, Macromolecular Rapid Communications, 2015, 36(20), 1816-1821

合成路线：1 步

反应条件：

1.1R:Cs2CO3, C:Pd(PPh3)4, S:THF, 3 d, 80°C

参考文献：

Enhancing Phase Separation and Photovoltaic Performance of All-Conjugated Donor-Acceptor Block Copolymers with Semifluorinated Alkyl Side Chains

By Lombeck, Florian et al, Macromolecules (Washington, 2015, 48(21), 7851-7860

合成路线：2 步

反应条件：

1.1R:t-BuCO2H, R:K2CO3, C:Pd(OAc)2, C:(C6H11)3P, S:AcNMe2, 90 h, 60°C
2.1R:K3PO4, C:657408-07-6, C:Pd2(dba)3, S:PhMe, 3 h, 80°C

参考文献：

Simple Synthesis of P(Cbz-alt-TBT) and PCDTBT by Combining Direct Arylation with Suzuki Polycondensation of Heteroaryl Chlorides

By Lombeck, Florian et al, Macromolecular Rapid Communications, 2015, 36(2), 231-237

合成路线：1 步

_90%

反应条件：

1.1R:Et4N+ OH-, C:(o-MeC6H4)3P, C:Pd2(dba)3, S:PhMe, rt → 95°C; 3 h, 95°C
1.2R:PhBr, 1 h, 95°C
1.3R:PhB(OH)2, S:PhMe, 1 h, heated

参考文献：

Conjugated Polymers a la Carte from Time-Controlled Direct (Hetero)Arylation Polymerization

By Morin, Pierre-Olivier et al, ACS Macro Letters, 2015, 4(1), 21-24

合成路线：1 步

反应条件：

1.1R:Disodium carbonate, C:Pd(PPh3)4, S:PhMe, 48 h, reflux; reflux → 50°C
1.2R:HCl, S:H2O, S:MeOH, 50°C

参考文献：

Synthesis and characterization of carbazole-benzothiadiazole-based conjugated polymers for organic photovoltaic cells with triazole in the main chain

By Lim, Eunhee, International Journal of Photoenergy, 2013, 607826, 8 pp.

合成路线：7 步

反应条件：

1.1R:Disodium carbonate, C:Pd(PPh3)4, S:Benzene, S:EtOH, 15 h, 85°C
2.1R:Bromosuccinimide, S:CHCl3, 48 h, rt
2.2R:H2O
1.1S:Et2O, S:THF, -78°C; 24 h, -78°C → rt
1.2R:MeOH, R:NH4Cl, S:H2O
2.1R:Me3N •HCl, R:Et3N, S:CH2Cl2, 0°C; 90 min, 0°C
2.2R:H2O
3.1R:KOH, S:DMSO, 2 h, rt; 24 h, rt
3.2R:H2O
4.1R:BuLi, S:THF, S:Me(CH2)4Me, -78°C; 6 h, -78°C
4.22 h, -78°C; -78°C → rt; 24 h, rt
4.3R:H2O
5.1R:Et4N+ OH-, C:Pd(PPh3)4, S:H2O, S:PhMe, 3 d, 120°C
5.2R:PhBr, 2 h, 120°C
5.3R:2 h, 120°C

参考文献：

A Versatile Approach to Organic Photovoltaics Evaluation Using White Light Pulse and Microwave Conductivity

By Saeki, Akinori et al, Journal of the American Chemical Society, 2012, 134(46), 19035-19042

合成路线：2 步

165190-76-1

反应条件：

1.1R:Bromosuccinimide, S:AcOH, 36 h, rt
1.2R:HCl, S:H2O, rt
2.1R:K2CO3, C:Pd(PPh3)4, S:PhMe, S:H2O, 3 d, 90°C
2.2R:PhB(OH)2, R:PhBr, S:PhMe, 12 h, 90°C

参考文献：

Incorporation of pyrene units to improve hole mobility in conjugated polymers for organic solar cells

By Kim, Ji-Hoon et al, Macromolecules (Washington, 2012, 45(21), 8628-8638

合成路线：1 步

_36%

反应条件：

1.1R:K2CO3, C:Pd(PPh3)4, S:H2O, S:PhMe, 40 min, 140°C

参考文献：

A Spectroscopic and DFT Study of the Electronic Properties of Carbazole-Based D-A Type Copolymers

By Reish, Matthew E. et al, Journal of Physical Chemistry C, 2012, 116(40), 21255-21266

合成路线：1 步

反应条件：

1.1R:Et4N+ OH-, C:(p-MeC6H4)3P, C:Pd2(dba)3, S:PhMe, 225 min, reflux
1.2R:PhBr, 1 d, reflux
1.3R:PhB(OH)2, S:PhMe, 1 d, reflux

参考文献：

Controlled nanomorphology of PCDTBT-fullerene blends via polymer end-group functionalization for high efficiency organic solar cells

By Shim, Chiyeoung et al, Chemical Communications (Cambridge, 2012, 48(57), 7206-7208

合成路线：1 步

_69%

反应条件：

1.1R:Et4N+ OH-, C:Pd(PPh3)4, S:H2O, S:PhMe, 48 h, 85°C
1.2

参考文献：

Study of Intramolecular Charge Complexation in Carbazole-based Donor-π-acceptor Copolymers

By Kim, Jinseck et al, Polymer Preprints (American Chemical Society, 2011, 52(2), 996

合成路线：1 步

反应条件：

1.1R:Et4N+ OH-, C:Pd(OAc)2, C:(C6H11)3P, S:H2O, S:PhMe, 24 h, > 50°C
1.2R:HCl, S:H2O, S:MeOH, 50°C

参考文献：

Bulk heterojunction polymer solar cells based on binary and ternary blend systems

By Park, Song Ju et al, Journal of Polymer Science, 2011, 49(20), 4416-4424

合成路线：1 步

1271797-47-7

反应条件：

1.1R:Et4N+ OH-, C:Pd(PPh3)4, S:H2O, S:PhMe, 48 h, 85°C

参考文献：

Parameters influencing the molecular weight of 3,6-carbazole-based D-π-A-type copolymers

By Fu, Yuanhe et al, Journal of Polymer Science, 2011, 49(20), 4368-4378

合成路线：1 步

反应条件：

1.1

参考文献：

Carbazole and thienyl benzo[1,2,5]thiadiazole based polymers with improved open circuit voltages and processability for application in solar cells

By Yi, Hunan et al, Journal of Materials Chemistry, 2011, 21(35), 13649-13656

合成路线：1 步

_70%