Recent results for synthesis of conjugated polymers, poly(arylene vinylene)s exemplified as poly(fluorene vinylene)s and poly(phenylene vinylene)s, by acyclic diene metathesis (ADMET) polymerization have been introduced. The methods using molybdenum and ruthenium catalysts afforded defect-free, high molecular weight polymers with all trans olefinic double bonds, and significant reduction of by-products (halogen, sulfur etc.) in addition of decrease of structurally defects have been attained. The methods also demonstrated precise synthesis of end-functionalized polymers that showed unique optical properties combined with the end groups. Catalytic one-pot syntheses of end-functionalized poly(9,9-dialkylfluorene-2,7-vinylene)s have been attained by both ruthenium (by chain-transfer) and molybdenum catalysts and the method should provide more green route for synthesis of conjugated materials with better device performance.
Skotheim, T. (2007) Handbook of Conducting Polymers. 3rd Edition, Reynolds, J. Ed., CRC Press, Boca Raton.
Jenekhe, S.A. (2004) Special Issue in Organic Electronics. Chemistry of Materials, 16, 4381-4842. https://doi.org/10.1021/cm041000r
Grimsdale, A.C., Chan, K.L., Martin, R.E., Jokisz, P.G. and Holmes, A.B. (2009) Synthesis of Light-Emitting Conjugated Polymers for Applications in Electroluminescent Devices. Chemical Reviews, 109, 897-1091. https://doi.org/10.1021/cr000013v
Burn, P.L., Bradley, D.D.C., Friend, R.H., Halliday, D.A., Holmes, A.B., Jackson, R.W. and Kraft, A. (1992)Precursor Route Chemistry and Electronic Properties of Poly(p-phenylenevinylene), Poly[(2,5-dimethyl-p-phenylene)vinylene], and Poly[(2,5-dimethoxy-p-phenylene)vinylene]. Journal of the Chemical Society, Perkin Transactions, 1, 3225-3231. https://doi.org/10.1039/p19920003225
van Breemen, A.J.J.M., Issaris, A.C., de Kok, M.M., van der Borght, M.J.A.N., Adriaensens, P.J., Gelan, J.M.J.V. and vander Zande, D.J.M. (1999) Optimization of the Polymerization Process of Sulfinyl Precursor Polymers toward Poly(p-phenylenevinylene). Macromolecules, 32, 5728-5735. https://doi.org/10.1021/ma9902246
Jin, S.-H., Park, H.-J., Kim, J.Y., Lee, K., Lee, S.-P., Moon, D.-K., Lee, H.-J. and Gal, Y.-S. (2002) Poly(fluorenevinylene) Derivative by Gilch Polymerization for Light-Emitting Diode Applications. Macromolecules, 35, 7532-7534. https://doi.org/10.1021/ma020671c
Jin, S.-H., Kang, S.-Y., Kim, M.-Y. and Chan, Y.U. (2003) Synthesis and Electroluminescence Properties of Poly(9,9-di-n-octylfluorenyl-2,7-vinylene) Derivatives for Light-Emitting Display. Macromolecules, 36, 3841-3847. https://doi.org/10.1021/ma0300490
Tsai, L.-R. and Chen, Y. (2008) Hyperbranched Poly(fluorenevinylene)s Obtained from Self-Polymerization of 2,4,7-Tris(bromomethyl)-9,9-dihexylfluorene. Macromolecules, 41, 5098-5106. https://doi.org/10.1021/ma800545z
Grisorio, R., Mastrorilli, P., Nobile, C.F., Romanazzi, G. and Suranna, G.P. (2005) A Novel Synthetic Protocol for Poly(fluorenylenevinylene)s: A Cascade Suzuki-Heck Reaction. Tetrahedron Letters, 46, 2555-2558. https://doi.org/10.1016/j.tetlet.2005.02.090
Mikroyannidis, J.A., Gibbons, K.M., Kulkarni, A.P. and Jenekhe, S.A. (2008) Poly(fluorenevinylene) Copolymers Containing Bis(phenyl)oxadiazole and Triphenylamine Moieties: Synthesis, Photophysics, and Redox and Electroluminescent Properties. Macromolecules, 41, 663-674.
Bao, Z., Chen, Y., Cai, R. and Yu, L. (1993) Conjugated Liquid-Crystalline Polymers Soluble and Fusible Poly(phenylenevinylene) by the Heck Coupling Reaction. Macromolecules, 26, 5281-5286. https://doi.org/10.1021/ma00072a002
Anuragudom, P., Newaz, S.S., Phanichphant, S. and Lee, T.R. (2006) Facile Horner-Emmons Synthesis of Defect-Free Poly(9,9-dialkylfluorenyl-2,7-vinylene). Macromolecules, 39, 3494-3499.
Liu, Q., Liu, W., Yao, B., Tian, H., Xie, Z., Geng, Y. and Wang, F. (2007) Synthesis and Chain-Length Dependent Properties of Monodisperse Oligo(9,9-di-n-octylfluorene-2,7-vinylene)s. Macromolecules, 40, 1851-1857.
Lehman, S.E.J. and Wagener, K.B. (2003) ADMET Polymerization. In: Grubbs, R.H., Ed., Handbook of Metathesis, Vol. 3, Wiley-VCH, Weinheim, 283-353.
Baughman, T.W. and Wagener, K.B. (2005) Recent Advances in ADMET Polymerization. In: Buchmeiser, M.R., Ed., Advances in Polymer Science, Vol. 176, Springer, Heidelberg, 1-42.
Berda, E.B. and Wagener, K.B. (2012) Advances in Acyclic Diene Metathesis Polymerization. In: Matyjaszewski, K. and Müllen, M., Eds., Polymer Science: A Comprehensive Reference, Vol. 5, Elsevier BV, Amsterdam, 195-216.
Berda, E.B. and Wagener, K.B. (2012) Recent Advances in ADMET Polycondensation Chemistry. In: Schluter, D., Hawker, C. and Sakamosto, J., Eds., Synthesis of Polymers; New Structures and Methods, Wiley-VCH, Weinhein, 587-600.
Atallah, P., Wagener, K.B. and Schulz, M.D. (2013) ADMET: The Future Revealed. Macromolecules, 46, 4735-4741. https://doi.org/10.1021/ma400067b
Haque, T. and Nomura, K. (2015) Acyclic Diene Metathesis (ADMET) Polymerization for Precise Synthesis of Defect-Free Conjugated Polymers with Well-Defined Chain Ends. Catalysts, 5, 500-517. https://doi.org/10.3390/catal5020500
Thorn-Csányi, E. and Kraxner, P. (1995) Synthesis of Soluble, All-Trans Poly(2,5-diheptyl-p-phenylenevinylene) via Metathesis Polycondensation. Macromolecular Rapid Communications, 16, 147-153.
Thorn-Csányi, E. and Kraxner, P. (1997) Investigations of Stable Molybdenum Carbene Complexes for the Metathesis Synthesis of Dialkylsubstituted Poly(p-phenylenevinylene)s (PPVs). Journal of Molecular Catalysis A, 115, 21-28. https://doi.org/10.1016/S1381-1169(96)00079-9
Thorn-Csányi, E. and Kraxner, P. (1997) All-Trans Oligomers of 2,5-Dialkyl-1,4-Phenylenevinylenes-Metathesis Preparation and Characterization. Macromolecular Chemistry and Physics, 198, 3827-3843. https://doi.org/10.1002/macp.1997.021981205
Thorn-Csányi, E. and Kraxner, P. (1998) Synthesis of Soluble All-Trans Oligomers of 2,5-Diheptyloxy-p-Phenylenevinylene via Olefin Metathesis. Macromolecular Rapid Communications, 19, 223-228. https://doi.org/10.1002/marc.1998.030190413
Schlick, H., Stelzer, F., Tasch, S. and Leising, G. (2000) Highly Luminescent Poly[(m-phenylenevinylene)-co-(p-phenylenevinylene)] Derivatives Synthesized via Metathesis Condensation (ADMET). Journal of Molecular Catalysis A, 160, 71-84. https://doi.org/10.1016/S1381-1169(00)00234-X
Thorn-Csányi, E. and Herzog, O. (2004) Synthesis of Higher, Trans Configured Oligomers of Diisoalkyloxysubstituted Divinylbenzenes (PV-Oligomers) via Metathesis Telomerization of the Corresponding Lower Oligomers. Journal of Molecular Catalysis A, 213, 123-128. https://doi.org/10.1016/j.molcata.2003.12.002
Joo, S.-H. and Jin, J.-I. (2004) All Hydrocarbon Main-Chain Thermotropic Liquid Crystalline Polymers, Poly(1,1’-biphenylene-4,4’-alkenediyl)s, Prepared by the ADMET Method and Their Hydrogenated Polymers, Poly(1,1’-Biphenylene-4,4’-Alkanediyl)s. Journal of Polymer Science Part A: Polymer Chemistry, 42, 1335-1349. https://doi.org/10.1002/pola.11061
Oakley, G.W. and Wagener, K. (2005) Solid-State Olefin Metathesis: ADMET of Rigid-Rod Polymers and Ring-Closing Metathesis. Macromolecular Chemistry and Physics, 206, 15-24. https://doi.org/10.1002/macp.200400137
Pecher, J. and Mecking, S. (2007) Nanoparticles from Step-Growth Coordination Polymerization. Macromolecules, 40, 7733-7735. https://doi.org/10.1021/ma702048t
Nomura, K., Morimoto, H., Imanishi, Y., Ramhani, Z. and Geerts, Y. (2001) Synthesis of High Molecular Weight trans-Poly(9,9-di-n-octylfluorene-2,7-vinylene) by the Acyclic Diene Metathesis Polymerization Using Molybdenum Catalysts. Journal of Polymer Science Part A: Polymer Chemistry, 39, 2463-2470. https://doi.org/10.1002/pola.1223
Nomura, K., Miyamoto, Y., Morimoto, H. and Geerts, Y. (2005) Acyclic Diene Metathesis Polymerization of 2,5-Dialkyl-1,4-Divinylbenzene with Molybdenum or Ruthenium Catalysts: Factors Affecting the Precise Synthesis of Defect-Free, High-Molecular-Weight trans-Poly(p-phenylene vinylene)s. Journal of Polymer Science Part A: Polymer Chemistry, 43, 6166-6177. https://doi.org/10.1002/pola.21104
Yamamoto, N., Ito, R., Geerts, Y. and Nomura, K. (2009) Synthesis of All-Trans High Molecular Weight Poly(n-alkylcarbazole-2,7-vinylene)s and Poly(9,9-dialkylfluorene-2,7-vinylene)s by Acyclic Diene Metathesis (ADMET) Polymerization Using Ruthenium-Carbene Complex Catalysts. Macromolecules, 42, 5104-5111. https://doi.org/10.1021/ma900775x
Weychardt, H. and Plenio, H. (2008) Acyclic Diene Metathesis Polymerization of Divinylarenes and Divinylferrocenes with Grubbs-Type Olefin Metathesis Catalysts. Organometallics, 27, 1479-1485. https://doi.org/10.1021/om701277p
Qin, Y. and Hillmyer, M.A. (2009) Poly(3-hexyl-2,5-thienylene Vinylene) by ADMET Polymerization of a Dipropenyl Monomer. Macromolecules, 42, 6429-6432. https://doi.org/10.1021/ma9009824
Delgado, P.A., Liu, D.Y., Kean, Z. and Wagener, K.B. (2011) Synthesis of Poly(3-Dodecyl-2,5-Thienylene Vinylene) by Solid-State Metathesis Polycondensation. Macromolecules, 44, 9529-9532. https://doi.org/10.1021/ma2020529
Speros, J.C., Paulsen, B.D., White, S.P., Wu, Y., Jackson, E.A., Slowinski, B.S., Frisbie, C.D. and Hillmyer, M.A. (2012) An ADMET Route to Low-Band-Gap Poly(3-hexadecylthienylene Vinylene): A Systematic Study of Molecular Weight on Photovoltaic Performance. Macromolecules, 45, 2190-2199. https://doi.org/10.1021/ma3000434
Speros, J.C., Paulsen, B.D., Slowinski, B.S., Frisbie, C.D. and Hillmyer, M.A. (2012) Band Gap And HOMO Level Control in Poly(thienylene vinylene)s Prepared by ADMET Polymerization. ACS Macro Letters, 1, 986-990. https://doi.org/10.1021/mz300326k
Speros, J.C., Martinez, H., Paulsen, B.D., White, S.P., Bonifas, A.D., Goff, P.C., Frisbie, C.D. and Hillmyer, M.A. (2013) Effects of Olefin Content and Alkyl Chain Placement on Optoelectronic and Morphological Properties in Poly(thienylene vinylenes). Macromolecules, 46, 5184-5194. https://doi.org/10.1021/ma4009115
Zhang, Z. and Qin, Y. (2015) Synthesis and Characterization of Poly(selenylene vinylene) and Poly(selenylene vinylene)-co-poly(thienylene vinylene) through Acyclic Diene Metathesis (ADMET) Polymerization. ACS Macro Letters, 4, 679-683. https://doi.org/10.1021/acsmacrolett.5b00292
Zhang, Z. and Qin, Y. (2016) Structurally Diverse Poly(thienylene vinylene)s (PTVs) with Systematically Tunable Properties through Acyclic Diene Metathesis (ADMET) and Postpolymerization Modification. Macromolecules, 49, 3318-3327. https://doi.org/10.1021/acs.macromol.6b00502
Nomura, K., Yamamoto, N., Ito, R., Fujiki, M. and Geerts, Y. (2008) Exclusive End Functionalization of All-Trans Poly(fluorene vinylene)s Prepared by Acyclic Diene Metathesis Polymerization: Facile Efficient Synthesis of Amphiphilic Triblock Copolymers by Grafting Poly(ethylene glycol). Macromolecules, 41, 4245-4249. https://doi.org/10.1021/ma800558p
Kuwabara, S., Yamamoto, N., Sharma, P.M.V., Takamizu, K., Fujiki, M., Geerts, Y. and Nomura, K. (2011) Precise Synthesis of Poly(fluorene-2,7-vinylene)s Containing Oligo(thiophene)s at the Chain Ends: Unique Emission Properties by the End Functionalization. Macromolecules, 44, 3705-3711. https://doi.org/10.1021/ma200638a
Abdellatif, M.M. and Nomura, K. (2012) Precise Synthesis of Amphiphilic Multiblock Copolymers by Combination of Acyclic Diene Metathesis (ADMET) Polymerization with Atom Transfer Radical Polymerization (ATRP) and Click Chemistry. ACS Macro Letters, 1, 423-427. https://doi.org/10.1021/mz300061a
Takamizu, K., Inagaki, A. and Nomura, K. (2013) Precise Synthesis of Poly(fluorene vinylene)s Capped with Chromophores: Efficient Fluorescent Polymers Modified by Conjugation Length and End-Groups. ACS Macro Letters, 2, 980-984. https://doi.org/10.1021/mz400455b
Nomura, K., Haque, T., Onuma, T., Hajjaj, F., Asano, M.S. and Inagaki, A. (2013) Precise One-Pot Synthesis of End-Functionalized Conjugated Multi-Block Copolymers via Combined Olefin Metathesis and Wittig-Type Coupling.Macromolecules, 46, 9563-9574. https://doi.org/10.1021/ma4022554
Nomura, K., Haque, T., Miwata, T., Inagaki, A. and Takamizu, K. (2015) Precise One-Pot Synthesis of Fully Conjugated End Functionalized Star Polymers Containing Poly(fluorene-2,7-vinylene) (PFV) Arms. Polymer Chemistry, 6, 380-388. https://doi.org/10.1039/C4PY01287A
Nomura, K. and Abdellatif, M.M. (2010) Precise Synthesis of Polymers Containing Functional End Groups by Living Ring-Opening Metathesis Polymerization (ROMP): Efficient Tools for Synthesis of Block/Graft Copolymers. Polymer, 51, 1861-1881. https://doi.org/10.1016/j.polymer.2010.02.028
Abdellatif, M.M. and Nomura, K. (2013) Precise Synthesis of End-Functionalized Oligo(2,5-dialkoxy-1,4-phenylene vinylene)s with Controlled Repeat Units via Combined Olefin Metathesis and Wittig-type Coupling. Organic Letters, 15, 1618-1621. https://doi.org/10.1021/ol400397p
Abdellatif, M.M., Yorsaeng, S., Inagaki, A. and Nomura, K. (2014) Synthesis of End Functionalized Oligo(2,5-dialkoxy-1,4-phenylene vinylene)s. Macromolecular Chemistry and Physics, 215, 1973-1983. https://doi.org/10.1002/macp.201400163
Hillmyer, M.A., Nguyen, S.B.T. and Grubbs, R.H. (1997) Utility of a Ruthenium Metathesis Catalyst for the Preparation of End-Functionalized Polybutadiene. Macromolecules, 30, 718-721. https://doi.org/10.1021/ma961316n
Pitet, L.M. and Hillmyer, M.A. (2011) Carboxy-Telechelic Polyolefins by ROMP Using Maleic Acid as a Chain Transfer Agent. Macromolecules, 44, 2378-2381. https://doi.org/10.1021/ma102975r
Lin, T.-W., Chou, C.-M., Lin, N.-T., Lin, C.-L. and Luh, T.-Y. (2014) End Group Modification of Polynorbornenes. Macromolecular Chemistry and Physics, 215, 2357-2364. https://doi.org/10.1002/macp.201400284
Miyashita, T. and Nomura, K. (2016) Catalytic One-Pot Synthesis of End-Functionalized Poly(9,9’-di-n-octylfluorenevinylene)s by Acyclic Diene Metathesis (ADMET) Polymerization Using Ruthenium-Carbene Catalysts. Macromolecules, 49, 518-526. https://doi.org/10.1021/acs.macromol.5b02287
Miyashita, T., Inagaki, A. and Nomura, K. (2016) One-Pot Synthesis of End-Functionalized Conjugated Polymers by Combined Acyclic Diene Metathesis (ADMET) Polymerization with Wittig-Type Coupling. Journal of the Japan Petroleum Institute, 59, 197-203. https://doi.org/10.1627/jpi.59.197