Reduced excimer formation in polyfluorenes by introducing coil-like poly[penta(ethylene glycol) methyl ether methacrylate] block segments

The formation of the aggregate and excimer in light-emitting polyfluorenes during annealing at high temperatures was reduced by adding coil-like block segments through atom transfer radical polymerization (ATRP), initialized by 2- bromoisobutyrate end-capped PF macroinitiator using CuBr/N,N,N',N',N''-pentamethyldiethylenetriamine (PMDETA) catalyst system. The rod-like macroinitiator was synthesized by the Yamamoto-type coupling using a Ni(COD)2 catalyst. The structure and physical properties were characterized by 1H NMR, thermal analysis, GPC, photoluminescence, small angle X-ray scattering and transmission electron microscopy. The addition of the coil-like block segments to the rod-like block segment resulted in the microphase separation between the component blocks which decreased the effective conjugation length of the conjugated moieties. The photoluminescence spectra measured from the thin films of the block copolymers revealed that the coil-like endblocks, attached to the conjugated block segments, suppressed the excimer formation of the PF molecules during annealing at high temperature.

[1]  S. Beaupré,et al.  Light-emitting diodes from fluorene-based π-conjugated polymers , 2000 .

[2]  G. Klaerner,et al.  Polyfluorene Derivatives: Effective Conjugation Lengths from Well-Defined Oligomers , 1998 .

[3]  K. Müllen,et al.  End-Functionalization of Poly-(2,7-Fluorene): A Key Step Towards Novel Luminescent Rod-Coil Block Copolymers , 1999 .

[4]  S. Chua,et al.  Synthesis of Conjugated−Ionic Block Copolymers by Controlled Radical Polymerization , 2003 .

[5]  J. C. Scott,et al.  Cross-linkable Polymers Based on Dialkylfluorenes , 1999 .

[6]  Gerrit Klaerner,et al.  Oxidative Stability and Its Effect on the Photoluminescence of Poly(Fluorene) Derivatives: End Group Effects , 1999 .

[7]  S. Beaupré,et al.  Molecular Design and Characterization of Chromic Polyfluorene Derivatives , 2000 .

[8]  W. Zin,et al.  Nanoscale Organization of Conjugated Rods in Rod-Coil Molecules** , 2001 .

[9]  Robert D. Miller,et al.  Colorfast Blue‐Light‐Emitting Random Copolymers Derived from Di‐n‐hexylfluorene and Anthracene , 1998 .

[10]  Luping Yu,et al.  Syntheses of Oligophenylenevinylenes-Polyisoprene Diblock Copolymers and Their Microphase Separation , 1999 .

[11]  J. C. Scott,et al.  Thermally Stable Blue-Light-Emitting Copolymers of Poly(alkylfluorene) , 1998 .

[12]  V. Urban,et al.  Syntheses of Amphiphilic Diblock Copolymers Containing a Conjugated Block and Their Self-Assembling Properties , 2000 .

[13]  Tomasz Kowalewski,et al.  Tuning the electrical conductivity and self-assembly of regioregular polythiophene by block copolymerization: nanowire morphologies in new di- and triblock copolymers. , 2002, Angewandte Chemie.

[14]  Yongye Liang,et al.  Conjugated block copolymers and co-oligomers: from supramolecular assembly to molecular electronics , 2007 .

[15]  W. R. Salaneck,et al.  Electroluminescence in conjugated polymers , 1999, Nature.

[16]  Mena-Osteritz,et al.  Two-Dimensional Crystals of Poly(3-Alkyl- thiophene)s: Direct Visualization of Polymer Folds in Submolecular Resolution This work was supported by the European Union in the framework of Frequent-Esprit 24793. , 2000, Angewandte Chemie.