evidence that the polymerization goes through a chain-growth mechanism unlike
other polycondensation reactions, with Yokozawa renaming the polymerization as
the Kumada catalyst transfer polycondensation (KCTP). Mechanistic efforts into
understanding the mechanism for obtaining absolute control were led by the groups
of McCullough, Yokozawa, Kiriy, and McNeil. Kiriy proposed an external initiation method for growing P3HT grafts on polymers immobilized on surfaces.
Further efforts at external initiation were led by the groups of Kiriy and Luscombe
in attempts to obtain absolute control over the chain-growth mechanism for the
synthesis of polymers with well-controlled molecular weights and narrow polydispersity indexes. The external initiation technique was further extended to initiation
of polymerizations from surfaces such as gold, silica, and ITO. An environmentally
stable P3MT layer was grown on ITO surfaces by the groups of Luscombe and
Locklin and the latter further showed that this P3MT layer can probably replace the
PEDOT:PSS interlayer in organic solar cells. The Kiriy and Luscombe groups took
advantage of the robust chain-growth mechanism of GRIM/KCTP to synthesize
star-shaped polymers using a core-first approach. Luscombe’s group demonstrated
that V-shaped and Y-shaped polymers could be synthesized with good control over
molecular weights and narrow polydispersities. Further improvements in structure
and functionality can be achieved by designing more complex architectures tuned
for specific applications.
References
1. Tourillon G, Garnier F (1983) Stability of conducting polythiophene and derivatives.
J Electrochem Soc 130:2042–2044
2. McCullough RD, Ewbank PC (1998) Regioregular, head-to-tail coupled poly
(3-alkylthiophene) and its derivatives. In: Skotheim TA, Elsenbaumer RL, Reynolds JR
(eds) Handbook of conducting polymers, 2nd edn, revised and expanded. Marcel Dekker,
New York, pp 255-258
3. Jeffries-El M, McCullough RD (2007) Regioregular polythiophenes. In: Skotheim TA,
Reynolds JR (eds) Handbook of conducting polymers, 3rd edn, Conjugated polymers
processing and applications. CRC, Boca Raton, pp 1–49
4. McCullough RD (1999) The chemistry of conducting polythiophenes: from synthesis to selfassembly to intelligent materials. In: Fichou D (ed) Handbook of oligo- and polythiophenes.
Wiley-VCH, Weinheim
5. Schopf G, Kossmehl G (1997) Polythiophenes – electrically conductive polymers. Adv
Polym Sci 129:1–166
6. Ewbank PC, Stefan MC, Sauve G, McCullough RD (2009) In: Perepichka IF, Perepichka DF
(eds) Handbook of thiophene-based materials: applications in organic electronics and photonics, vol 1: synthesis and theory. Wiley, West Sussex
7. McCullough RD (1998) The chemistry of conducting polythiophenes. Adv Mater 10:93–116
8. Perepichka IF, Perepichka DF, Meng H, Wudl F (2005) Light-emitting polythiophenes. Adv
Mater 17:2281–2305
9. Roncali J (1992) Conjugated poly(thiophenes): synthesis, functionalization, and applications.
Chem Rev 92:711–738
10. Roncali J (1997) Synthetic principles for bandgap control in linear π-conjugated systems.
Chem Rev 97:173–205
Progress in the Synthesis of Poly(3-hexylthiophene)
27
other polycondensation reactions, with Yokozawa renaming the polymerization as
the Kumada catalyst transfer polycondensation (KCTP). Mechanistic efforts into
understanding the mechanism for obtaining absolute control were led by the groups
of McCullough, Yokozawa, Kiriy, and McNeil. Kiriy proposed an external initiation method for growing P3HT grafts on polymers immobilized on surfaces.
Further efforts at external initiation were led by the groups of Kiriy and Luscombe
in attempts to obtain absolute control over the chain-growth mechanism for the
synthesis of polymers with well-controlled molecular weights and narrow polydispersity indexes. The external initiation technique was further extended to initiation
of polymerizations from surfaces such as gold, silica, and ITO. An environmentally
stable P3MT layer was grown on ITO surfaces by the groups of Luscombe and
Locklin and the latter further showed that this P3MT layer can probably replace the
PEDOT:PSS interlayer in organic solar cells. The Kiriy and Luscombe groups took
advantage of the robust chain-growth mechanism of GRIM/KCTP to synthesize
star-shaped polymers using a core-first approach. Luscombe’s group demonstrated
that V-shaped and Y-shaped polymers could be synthesized with good control over
molecular weights and narrow polydispersities. Further improvements in structure
and functionality can be achieved by designing more complex architectures tuned
for specific applications.
References
1. Tourillon G, Garnier F (1983) Stability of conducting polythiophene and derivatives.
J Electrochem Soc 130:2042–2044
2. McCullough RD, Ewbank PC (1998) Regioregular, head-to-tail coupled poly
(3-alkylthiophene) and its derivatives. In: Skotheim TA, Elsenbaumer RL, Reynolds JR
(eds) Handbook of conducting polymers, 2nd edn, revised and expanded. Marcel Dekker,
New York, pp 255-258
3. Jeffries-El M, McCullough RD (2007) Regioregular polythiophenes. In: Skotheim TA,
Reynolds JR (eds) Handbook of conducting polymers, 3rd edn, Conjugated polymers
processing and applications. CRC, Boca Raton, pp 1–49
4. McCullough RD (1999) The chemistry of conducting polythiophenes: from synthesis to selfassembly to intelligent materials. In: Fichou D (ed) Handbook of oligo- and polythiophenes.
Wiley-VCH, Weinheim
5. Schopf G, Kossmehl G (1997) Polythiophenes – electrically conductive polymers. Adv
Polym Sci 129:1–166
6. Ewbank PC, Stefan MC, Sauve G, McCullough RD (2009) In: Perepichka IF, Perepichka DF
(eds) Handbook of thiophene-based materials: applications in organic electronics and photonics, vol 1: synthesis and theory. Wiley, West Sussex
7. McCullough RD (1998) The chemistry of conducting polythiophenes. Adv Mater 10:93–116
8. Perepichka IF, Perepichka DF, Meng H, Wudl F (2005) Light-emitting polythiophenes. Adv
Mater 17:2281–2305
9. Roncali J (1992) Conjugated poly(thiophenes): synthesis, functionalization, and applications.
Chem Rev 92:711–738
10. Roncali J (1997) Synthetic principles for bandgap control in linear π-conjugated systems.
Chem Rev 97:173–205
Progress in the Synthesis of Poly(3-hexylthiophene)
27