Polythiophene self-assembly

Regioregular polythiophenes self-assembled by hydrogen bonding... 

FIGURE 17.13 Example of x-ray diffraction profile from an alternating alkyl/fluoroalkyl- and alkyl/perfluoralkyl-substituted polythiophenes. The specific side chains are (CH2)5(CF2)CF3 alternating with (CFl2)8CH3. Here, the polythiophene self-assembles into a bilayer repeat. (Adapted from Dong, X.M. and Collard, D.M., Macromolecules, 33, 6916, 2000. With permission.)... 

Liu, J., Sheina, E., Kowalewski, T. and McCullough, R. D. (2002) Tuning the electrical conductivity and self-assembly of regioregular polythiophene by block... 

R.D. McCullough, P.C. Ewbank, and R.S. Loewe, Self-assembly and disassembly of regioregular, water soluble polythiophenes chemoselective ionchromatic sensing in water, J. Am. Chem. Soc., 119 633-634, 1997. 

Nilsson KPR, Rydberg J, Baltzer L, Inganas O (2003) Self-assembly of synthetic peptides control conformation and optical properties of a zwitterionic polythiophene derivative. Proc Natl Acad Sci 100 10170-10174... 

Dannetun P, Boman M, Stafstrom S, Salaneck WR, Lazzaroni R, Fredriksson C, Bredas JL, Zamboni R, Taliani C (1993) The chemical and electronic structure of the interface between aluminum and polythiophene semiconductors. J Chem Phys 99(l) 664-672 Ahn H, Whitten JE (2003) Vapor-deposition of aluminum on thiophene-terminated self-assembled monolayers on gold. J Phys Chem B 107(27) 6565-6572 Fisher GL, Flooper A, Opila RL, Jung DR, Allara DL, Winograd N (1999) The interaction between vapor-deposited A1 atoms and methylester-terminated self-assembled monolayers studied by time-of-flight secondary ion mass spectrometry, X-ray photoelectron spectroscopy and infrared reflectance spectroscopy. J Electron Spectrosc Relat Phenom 98-99 139-148... 

Swager and coworkers also applied the self-assembly process in side-chain systems [131, 132]. The bisphenylene crown ether was incorporated into a conjugated backbone, polyphenyleneacetylene 87. This polymer complexes with paraquat 88 to give a novel polyrotaxane structure (89). With a polythiophene backbone, a similar polyrotaxane was synthesized by the same approach. 

Molecular self-organization in solution depends critically on molecular structural features and on concentration. Molecular self-organization or aggregation in solution occurs at the critical saturation concentration when the solvency of the medium is reduced. This can be achieved by solvent evaporation, reduced temperature, addition of a nonsolvent, or a combination of all these factors. Solvato-chromism and thermochromism of conjugated polymers such as regioregular polythiophenes are two illustrative examples, respectively, of solubility and temperature effects [43-45]. It should therefore be possible to use these solution phenomena to pre-establish desirable molecular organization in the semiconductor materials before deposition. Our studies of the molecular self-assembly behavior of PQT-12, which leads to the preparation of structurally ordered semiconductor nanopartides [46], will be described. These PQT-12 nanopartides have consistently provided excellent FETcharacteristics for solution-processed OTFTs, irrespective of deposition methods. 

Fig. 33 Schematic illustration of self-assembly of a chiral supramolecule from nonchiral polythiophene polyanion 81 and random coil synthetic peptide 82...

Nilsson, K.P., Rydberg, J., Baltzer, L., and Inganas, O. "Twisting macromolecular chains self-assembly of a chiral supermolecule from nonchiral polythiophene polyanions and random-coil synthetic peptides". Proc. Natl. Acad. Sci. U.S.A. 101(31), 11197-11202 (2004). 

Reitzel, N. et al.. Self-assembly of conjugated polymers at the air/water interface. Structure and properties of Langmuir and Langmuir-Blodgett films of amphiphilic regioregular polythiophenes, J. Am. Chem. Soc. 122, 5788-5800, 2000. de Boer, B. et al.. Amphiphilic, regioregular polythiophenes. Macromolecules 35, 6883-6892, 2002. 

Kim, D.H. et al.. Single-crystal polythiophene microwires grown by self-assembly, Adv. Mater. 18, 719, 2006. 

R. Verduzco, I. Botiz, D. L. Pickel, S. M. Kilbey, K. Hong, E. Dimasi, S. B. Darling, Polythiophene-BZocfc-Polyfluorene and Polythiophene-B/ocfc-Poly(Fluorene-co-Benzothiadiazole) Insights into the Self-Assembly of All-Conjugated Block Copolymers. Macromolecules 2011,44, 530-539. 

FIGURE 9.7 Carboxylic acid derivatives of regioregular polythiophene (Table 9.1, entry 17) can act as sensors of alkali metals in water through a self-assembly and disassembly mechanism. 

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