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 IJOC  Vol.6 No.1 , March 2016
Synthesis and Photophysical Properties of Fluorene or Carbazole-Based Alternating Copolymers Containing Si and Ethynylene Units in the Main Chain
Abstract: Alternating copolymerization of 9,9-dihexyl-2,7-dibromofluorene, N-hexyl-2,7-dibromocarbazole (HCz) with diethynyldimethylsilane, diethynyldiphenylsilane, has been investigated using Sonogashira coupling reaction. Photophysical properties of the resulting copolymers were investigated with UV-Vis absorption and photoluminescence spectroscopy. All the copolymers in chloro-form solution showed absorption peaks at 270 - 280 nm with shoulder peaks at around 380 nm derived from π-π* transition or intra-molecular charge transfer through σ-π moiety, respectively. The chloroform solutions of the copolymers showed broad emission peaks at 415 - 425 nm. The emission wave lengths of the copolymers in the solid state (cast film) detected at 360 - 385 nm were remarkably blue-shifted in comparison with those in the chloroform solutions. Hydrosilylation reaction of the copolymers with 1,4-bis(dimethylsilyl)benzene yielded networked copolymers soluble in chloroform, indicating formation of branching polymers. The chloroform solutions of the HCz-based networked copolymers showed bimodal emission derived from new highly energy states in the σ-π conjugation.
Cite this paper: Naga, N. , Tagaya, N. and Tomoda, H. (2016) Synthesis and Photophysical Properties of Fluorene or Carbazole-Based Alternating Copolymers Containing Si and Ethynylene Units in the Main Chain. International Journal of Organic Chemistry, 6, 20-30. doi: 10.4236/ijoc.2016.61003.
References

[1]   Facchetti, A. (2011) π-Coujugated Polymers for Organic Electronics and Photovolatic Cell Applications. Chemistry of Materials, 23, 733-758.
http://dx.doi.org/10.1021/cm102419z

[2]   Saleh, M., Alam, J., Dass, L.A. and Raja, M. (2011) Recent Advances in Conjugated Polymers for Light Emitting Devices. International Journal of Molecular Science, 12, 2036-2054.

[3]   Kim, H.K., Ryu, M.K. and Lee, S.M. (1997) Novel Silicon-Containing Poly(p-phenylenevinylene)-Related Polymers: Synthesis and Optical Properties. Macromolecules, 30, 1236-1239.
http://dx.doi.org/10.1021/ma961295x

[4]   Kwak, G. and Masuda, T. (2002) Poly(silyleneethynylenephenylene) and Poly(silylenepheny-leneethynylenephenylene)s: Synthesis and Photophysical Properties Related to Charge Transfer. Macro-molecules, 35, 4138-4142.

[5]   Kim, H.K., Paik, K.L., Baek, N.S., Lee, Y. and Yoshino, K. (2003) Novel Silicon-Based Alternating Copolymers: Synthesis, Photophysical Properties, and Tunable EL Colors. Macromolecular Symposia, 192, 135-149.
http://dx.doi.org/10.1002/masy.200390022

[6]   Rao, T.V., Yamashita, H., Uchimaru, Y., Sugiyama, J. and Takeuchi, K. (2005) Pd-Catalyzed Hydrosilylation Polymerization of a Dihydrosilane with Diyne/Triyne Mixed Systems Affording Crosslinked Silylene-Divinylene Polymers and Their Properties. Polymer, 46, 9736-9741.
http://dx.doi.org/10.1016/j.polymer.2005.08.052

[7]   Yamashita, H., de Leon, M.S., Channasanon, S., Suzuki, Y., Uchimaru, Y. and Takeuchi, K. (2003) Palladium-Catalyzed Hydrosilylation Polymerization of Dihydro Silanes with Diyne Affording Silylene-Divinylene Polymers. Polymer, 55, 7089-7093.
http://dx.doi.org/10.1016/j.polymer.2003.09.003

[8]   Kitamura, N. and Yamamoto, T. (2004) Silicon-Containing Polymers or Oligomers for Electroluminescent Devices and Their Manufacture. JP2004-131700A.

[9]   Takagi, K., Tahara, A. and Kakiuchi, H. (2009) Synthesis and Light-Emitting Behavior of Silicon-Bridged Fluorene Copolymers Bearing Oli-goarylenevinylene Chromophore. Polymer Journal, 41, 733-738.
http://dx.doi.org/10.1295/polymj.PJ2009088

[10]   Takagi, K., Kakiuchi, H. and Suzuki, M. (2006) Synthesis of Fluorene-Based Light-Emitting Polymers Bearing Silane Units and Their Opteolectornic Properties. Kohbunshi Ronbunsyu, 63, 663-669.
https://www.jstage.jst.go.jp/article/koron/63/10/63_10_663/_pdf

[11]   Kobayashi, N. and Kijima, M. (2007) Microporous Materials Derived from Two- and Three-Dimensional Hyperbranched Conjugated Polymers by Thermal Elimination of Substituents. Journal of Materials Chemistry, 17, 4289- 4296.
http://dx.doi.org/10.1039/b707925g

[12]   Shao, K.F., Xu, X.J., Liu, Y.Q. and Yang, L.M. (2006) Blue Electrophosphorescent Light-Emitting Device Using a Novel Nonconjugated Polymer as Host Materials. Chemistry Letters, 35, 404-405.
http://dx.doi.org/10.1246/cl.2006.404

[13]   Fang, M.C., Watanabe, A. and Matsuda, M. (1996) Emission Spectra of σ-π-Conjugated Organosilicon Copolymers Consisting of Alternating Dimethylsilylene and Aromatic Units. Macromolecules, 29, 6807-6813.
http://dx.doi.org/10.1021/ma960398c

[14]   Kim, K.D., Park, J.S. and Kim, H.K. (1998) Blue Electroluminescence from Novel Silicon-Containing Poly(Cyanoterephthalylidene) Copolymers. Macromolecules, 31, 7267-7272.
http://dx.doi.org/10.1021/ma980349v

[15]   Naga, N., Tagaya, N., Noda, H., Imai, T. and Tomoda, H. (2008) Synthesis and Properties of Fluorene or Carbazole- Based Alternating Copolymers Containing Si and Vinylene Units in the Main Chain. Journal of Polymer Science: Part A: Polymer Chemistry, 46, 4513-4521.
http://dx.doi.org/10.1002/pola.22788

[16]   Naga, N., Ohkura, Y., Tagaya, N. and Tomoda, H. (2011) Synthesis and Chemosensing Behavior of Fluorene-Based Alternating Copolymers Containing Ether Side Chains and Si-Vinylene Units in the Main Chain. Journal of Polymer Science: Part A: Polymer Chemistry, 49, 4935-4940.
http://dx.doi.org/10.1002/pola.24943

[17]   Wang, F., Kaafarani, B.R. and Neckers, D.C. (2003) Synthesis of Silicon-Containing Unsaturated Polymers by Hydrosilylation Reactions. Photophysical Studies. Macromolecules, 36, 8225-8230.
http://dx.doi.org/10.1021/ma034618f

[18]   Kokil, A., Huber, C., Caseri, W.R. and Weder, C. (2003) Synthesis of π-Conjugated Organometallic Polymer Networks. Macromolecular Chemistry and Physics, 204, 40-45.
http://dx.doi.org/10.1002/macp.200290054

[19]   Kunai, A., Toyoda, E., Nagamoto, I., Horio, T. and Ishikawa, M. (1996) Polymeric Organosilicon Systems. 25. Preparation of Branched Polymers by Regiospecific Hydrosilylation of Poly[(silylene)diethynylenes] and Their Properties. Organometallics, 15, 75-83.
http://dx.doi.org/10.1021/om950322p

[20]   Sonntag, M. and Strohriegl, P. (2004) Novel 2,7-Linked Carbazole Trimers as Model Compounds for Conjugated Carbazole Polymers. Chemistry of Materials, 16, 4736-4742.
http://dx.doi.org/10.1021/cm040142i

 
 
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