Direct Synthesis of Chain-end-functionalized Poly(3-hexylthiophene) without Protecting Groups Using a Zincate Complex.

Chain-end-functionalized poly(3-hexylthiophene)s (P3HTs) with benzyl alcohol (─PhCH2 OH), phenol (─PhOH), and benzoic acid (─PhCOOH) groups are directly synthesized based on the Negishi catalyst-transfer polycondensation method utilizing the zincate complex of t Bu4 ZnLi2 . In this system, neither protection nor deprotection steps are required, and also providing a living polymerization system to control the molecular weight while maintaining a low molar mass dispersity (ÐM ) of the obtained P3HT derivatives. Indeed, the chain-end-functionalized P3HTs can be synthesized along with controlled number-average molecular weights (Mn = 5100-20 000), low ÐM (1.06-1.14), and high chain-end functionality (Fn = 46-86%). The Fn values for the alcohol and phenol groups are found to be high (86% for ─PhCH2 OH and 71% for ─PhOH based on 1 H NMR, respectively), as also confirmed by matrix-assisted laser desorption/ionization time of flight mass spectroscopy. The easily synthesizable chain-end-functionalized P3HTs will be applicable for the facile synthesis of block and branched polymers containing P3HT as well as its related semiconducting polymer segments.

[1]  Zhiqun Lin,et al.  A Facile and Highly Efficient Route to Amphiphilic Star-Like Rod-Coil Block Copolymer via a Combination of Atom Transfer Radical Polymerization with Thiol-Ene Click Chemistry. , 2020, Macromolecular rapid communications.

[2]  D. J. Nelson,et al.  Aldehydes and ketones influence reactivity and selectivity in nickel-catalysed Suzuki–Miyaura reactions†‡§ , 2019, Chemical science.

[3]  C. McNeill,et al.  Role of Molecular and Interchain Ordering in the Formation of a δ-Hole Transporting Layer in Organic Solar Cells. , 2019, ACS applied materials & interfaces.

[4]  Bumjoon J. Kim,et al.  Regioregular-block-Regiorandom Poly(3-hexylthiophene) Copolymers for Mechanically Robust and High-Performance Thin-Film Transistors , 2019, Macromolecules.

[5]  M. K. Bera,et al.  Simple synthesis of end functionalized regioregular poly(3‐hexyl thiophene) by catalytic‐initiated Kumada catalyst transfer polymerization , 2019, Journal of Polymer Science Part A: Polymer Chemistry.

[6]  Tomoya Higashihara.  Precise Synthesis of Block and Miktoarm Star‐Branched Polymers Containing Polythiophene Segments with Low Dispersity by Combination of Living Anionic Polymerization and Catalyst‐Transfer Polycondensation Systems , 2017 .

[7]  Koji Takagi,et al.  Termination reaction of living poly(3-hexylthiophene) using thiophene Grignard reagents: Substituent effect on the functionalization , 2017 .

[8]  M. Stefan,et al.  Enhancing Long-Range Ordering of P3HT by Incorporating Thermotropic Biphenyl Mesogens via ATRP , 2016 .

[9]  M. Teridi,et al.  A review of recent plasmonic nanoparticles incorporated P3HT: PCBM organic thin film solar cells , 2016 .

[10]  Tomoya Higashihara,et al.  Synthesis and Characterization of Multicomponent ABC- and ABCD-Type Miktoarm Star-Branched Polymers Containing a Poly(3-hexylthiophene) Segment. , 2016, ACS macro letters.

[11]  Tomoya Higashihara,et al.  Investigation of stoichiometry in reactants for atom-economical synthesis of regioregular poly(3-hexylthiophene) with low dispersity using zincate complex of tBu4ZnLi2 , 2016 .

[12]  K. Müllen,et al.  End Capping Does Matter: Enhanced Order and Charge Transport in Conjugated Donor-Acceptor Polymers , 2015 .

[13]  Tomoya Higashihara,et al.  Controlled Polymerization of Electron-deficient Naphthalene-diimide Containing Monomer by Negishi-type Catalyst-transfer Polymerization , 2015 .

[14]  C. Hawker,et al.  Exploring the synthesis and impact of end‐functional poly(3‐hexylthiophene) , 2015 .

[15]  Tomoya Higashihara,et al.  Synthesis and Characterization of ABC-Type Asymmetric Star Polymers Comprised of Poly(3-hexylthiophene), Polystyrene, and Poly(2-vinylpyridine) Segments , 2015 .

[16]  J. K. Park,et al.  Charge transport behaviors of end-capped narrow band gap polymers in bottom-contact organic field-effect transistors , 2014 .

[17]  C. Luscombe,et al.  Fully Conjugated Graft Copolymers Comprising a P-Type Donor–Acceptor Backbone and Poly(3-hexylthiophene) Side Chains Synthesized Via a “Graft Through” Approach , 2014 .

[18]  C. Luscombe,et al.  Simple procedure for mono- and bis-end-functionalization of regioregular poly(3-hexylthiophene)s using chalcogens. , 2014, Chemical communications.

[19]  H. Sirringhaus.  25th Anniversary Article: Organic Field-Effect Transistors: The Path Beyond Amorphous Silicon , 2014, Advanced materials.

[20]  E. Nesterov,et al.  One-Step Simple Preparation of Catalytic Initiators for Catalyst-Transfer Kumada Polymerization: Synthesis of Defect-Free Polythiophenes , 2014 .

[21]  H. Moon,et al.  Facile synthesis for well‐defined A2B miktoarm star copolymer of poly(3‐hexylthiophene) and poly(methyl methacrylate) by the combination of anionic polymerization and click reaction , 2013 .

[22]  Wen‐Chang Chen,et al.  Synthesis and Characterization of All-Conjugated Graft Copolymers Comprised of n-Type or p-Type Backbones and Poly(3-hexylthiophene) Side Chains , 2013 .

[23]  T. Michinobu,et al.  Synthesis and Postfunctionalization of Rod-Coil Diblock and Coil-Rod-Coil Triblock Copolymers Composed of Poly(3-hexylthiophene) and Poly(4-(4'-N,N-dihexylaminophenylethynyl)styrene) Segments , 2012 .

[24]  K. Hashimoto,et al.  End-group stannylation of regioregular poly(3-hexylthiophene)s , 2012 .

[25]  B. Sumpter,et al.  In Situ Formation of Pyridyl-Functionalized Poly(3-hexylthiophene)s via Quenching of the Grignard Metathesis Polymerization: Toward Ligands for Semiconductor Quantum Dots , 2012 .

[26]  C. Luscombe,et al.  Constructing Regioregular Star Poly(3-hexylthiophene) via Externally Initiated Kumada Catalyst-Transfer Polycondensation. , 2012, ACS macro letters.

[27]  Tomoya Higashihara,et al.  Purification-Free and Protection-Free Synthesis of Regioregular Poly(3-hexylthiophene) and Poly(3-(6-hydroxyhexyl)thiophene) Using a Zincate Complex of tBu4ZnLi2. , 2012, ACS macro letters.

[28]  W. Pisula,et al.  Enhanced mobility in P3HT-based OTFTs upon blending with a phenylene-thiophene-thiophene-phenylene small molecule. , 2012, Chemical communications.

[29]  J. Moon,et al.  End‐Capping Effect of a Narrow Bandgap Conjugated Polymer on Bulk Heterojunction Solar Cells , 2011, Advanced materials.

[30]  W. Huck,et al.  Convenient Route To Initiate Kumada Catalyst-Transfer Polycondensation Using Ni(dppe)Cl2 or Ni(dppp)Cl2 and Sterically Hindered Grignard Compounds , 2010 .

[31]  M. Thelakkat,et al.  Synthesis and Characterization of Monocarboxylated Poly(3-hexylthiophene)s via Quantitative End-Group Functionalization , 2010 .

[32]  Youngmin Lee,et al.  Facile Synthesis of Well-Defined Coil−Rod−Coil Block Copolymer Composed of Regioregular Poly(3-hexylthiophene) via Anionic Coupling Reaction , 2010 .

[33]  F. Krebs,et al.  "Hairy" poly(3-hexylthiophene) particles prepared via surface-initiated Kumada catalyst-transfer polycondensation. , 2009, Journal of the American Chemical Society.

[34]  T. Verbiest,et al.  Incorporation of Different End Groups in Conjugated Polymers Using Functional Nickel Initiators , 2009 .

[35]  Natalia V. Doubina,et al.  Effect of Initiators on the Kumada Catalyst-Transfer Polycondensation Reaction , 2009 .

[36]  M. Ueda,et al.  Well-Controlled Synthesis of Block Copolythiophenes , 2008 .

[37]  K. Hashimoto,et al.  Synthesis of all-conjugated diblock copolymers by quasi-living polymerization and observation of their microphase separation. , 2008, Journal of the American Chemical Society.

[38]  T. Yokozawa,et al.  Catalyst-Transfer Condensation Polymerization for the Synthesis of Well-Defined Polythiophene with Hydrophilic Side Chain and of Diblock Copolythiophene with Hydrophilic and Hydrophobic Side Chains , 2007 .

[39]  W. Su,et al.  Facile synthesis of well-defined block copolymers containing regioregular poly(3-hexyl thiophene) via anionic macroinitiation method and their self-assembly behavior. , 2007, Journal of the American Chemical Society.

[40]  M. Rawiso,et al.  Quasi-Controlled Polymerization through a Nickel Catalyst Process of a Functionalized Thiophene Monomer: Kinetic Studies and Application to the Synthesis of Regioregular Poly(thiophene-3-acetic acid) , 2007 .

[41]  Kentaro Tanaka,et al.  Toward a protecting-group-free halogen-metal exchange reaction: practical, chemoselective metalation of functionalized aromatic halides using dianion-type zincate, tBu4ZnLi2. , 2006, Journal of the American Chemical Society.

[42]  T. Yokozawa,et al.  Catalyst-transfer polycondensation. mechanism of Ni-catalyzed chain-growth polymerization leading to well-defined poly(3-hexylthiophene). , 2005, Journal of the American Chemical Society.

[43]  R. D. Mccullough,et al.  Facile Synthesis of End-Functionalized Regioregular Poly(3-alkylthiophene)s via Modified Grignard Metathesis Reaction , 2005 .

[44]  R. Gil,et al.  Experimental evidence for the quasi-living nature of the grignard metathesis method for the synthesis of regioregular poly(3-alkylthiophenes) , 2005 .

[45]  G. Kim,et al.  The application of soluble and regioregular poly(3-hexylthiophene) for organic thin-film transistors , 2005 .

[46]  N. Sedghi,et al.  A regioregular polyalkylthiophene bearing covalently-linked biotin, and its interaction with avidin in solution and in thin films. , 2004, Chemical communications.

[47]  R. D. Mccullough,et al.  In‐Situ End‐Group Functionalization of Regioregular Poly(3‐alkylthiophene) Using the Grignard Metathesis Polymerization Method , 2004 .

[48]  Darin W. Laird,et al.  Chain Growth Mechanism for Regioregular Nickel-Initiated Cross-Coupling Polymerizations , 2004 .

[49]  Tsutomu Yokozawa,et al.  Chain-growth polymerization for poly(3-hexylthiophene) with a defined molecular weight and a low polydispersity , 2004 .

[50]  R. D. Mccullough,et al.  End Group Modification of Regioregular Polythiophene through Postpolymerization Functionalization , 2002 .

[51]  Hajime Ito,et al.  First gold complex-catalysed selective hydrosilylation of organic compounds , 2000 .

[52]  Kazuya Tada,et al.  Photoinduced charge separation in photovoltaic cell with heterojunction of p- and n-type conjugated polymers , 1998 .