Skip to main content
SpringerLink
Log in

Liquid Crystalline Conjugated Polymers with Optoelectronic Functions

  • Reference work entry
  • First Online:
Liquid Crystalline Polymers

Part of the book series: Polymers and Polymeric Composites: A Reference Series ((POPOC))

  • 622 Accesses

Abstract

We review the recent progress in advanced functionalities of liquid crystalline polyacetylenes (LCPAs). We focus on properties and functionalities that include electrical anisotropy and linearly polarized luminescence (LPL). First, the synthesis of mono-substituted LCPAs using Fe-based Ziegler–Natta catalyst is briefly reviewed. The mono-LCPAs exhibit enantiotropic SA phases resulting from spontaneous orientation of the LC side chain. Iodine doping of mono-LCPA cast films followed by macroscopic alignment of the main chain accompanied by the side chain orientation using an external magnetic force of 0.7–1.0 T enhanced the electrical conductivity by two orders of magnitude to 10−6 S/cm and gave rise to a notable electrical anisotropy. Second, the synthesis of di-substituted LCPAs using metathesis catalyst that exhibit enantiotropically thermotropic or lyotropic liquid crystallinity is discussed. LC phases of di-LCPAs are assigned through observation of polarized optical microscope (POM) and differential scanning calorimeter (DSC) and measurements of X-ray diffraction (XRD). Using schematic energy levels of ground and low-lying excited states of non-, mono-, and di-PAs, the origin of the emission of substituted PAs is elucidated, and fluorescent trends including emission color are investigated. It is found that the macroscopically aligned films of the di-LCPAs emit LPL by virtue of the functionalities associated with liquid crystallinity and fluorescence. The aligned structures of the di-LCPAs are characterized in terms of main chain and side chain type alignments through XRD measurements of the macroscopically aligned polymer films. The mechanism of the LPL of the di-LCPAs with respect to the polymer structure, alignment type, and emission color is elucidated.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 329.99
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Hardcover Book
USD 449.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  • Akag K (2007) Synthesis and properties of liquid-crystalline-conjugated polymers. Bull Chem Soc Jpn 80:649–661

    Article  Google Scholar 

  • Akagi K (2009) Advances in liquid crystalline conjugated polymers. J Polym Sci A Polym Chem 47:2463–2485

    Article  CAS  Google Scholar 

  • Akagi K, Suezaki M, Shirakawa H, Kyotani H, Shimomura M, Tanabe Y (1989) Synthesis of polyacetylene films with high density and high mechanical strength. Synth Met 28:D1–D10

    Article  CAS  Google Scholar 

  • Akagi K, Goto H, Kadokura Y, Shirakawa H, Oh SY, Araya K (1995) Synthesis and properties of liquid crystalline polyacetylene derivatives. Synth Met 69:13–16

    Article  CAS  Google Scholar 

  • Choi SK, Gal YS, Jin SH, Kim HK (2000) Poly(1,6-heptadiyne)-based materials by metathesis polymerization. Chem Rev 100:1645–1682

    Article  CAS  PubMed  Google Scholar 

  • Dierking I (2003) Textures of liquid crystals. Wiley-VCH, Weinheim

    Google Scholar 

  • Ghosh H, Shukla A, Mazumdar S (2000) Electron-correlation-induced transverse delocalization and longitudinal confinement in excited states of phenyl-substituted polyacetylenes. Phys Rev B 62(19):12763–12774

    Article  CAS  Google Scholar 

  • Goto H, Dai X, Ueoka T, Akagi K (2004) Synthesis and properties of polymers from monosubstituted acetylene derivatives bearing ferroelectric liquid crystalline groups. Macromolecules 37:4783–4793

    Article  CAS  Google Scholar 

  • Hidayat R, Fujii A, Ozaki M, Teraguchi M, Masuda M, Yoshino K (2001) Exciton dynamics in disubstituted polyacetylenes. Synth Met 119:597–598

    Article  CAS  Google Scholar 

  • Ho MS, Hsu CS (2009) Synthesis and hierarchical superstructures of side chain liquid crystal polyacetylenes containing galactopyranoside end groups. J Polym Sci A Polym Chem 47:6596–6611

    Article  CAS  Google Scholar 

  • Huang C, Yang S, Chen K, Hsu CS (2006) Synthesis and light emitting properties of polyacetylenes having pendent fluorene groups. J Polym Sci Part A Polym Chem 44:519–531

    Article  CAS  Google Scholar 

  • Koltzenburg S, Wolff D, Stelzer F, Springer J, Nuyken O (1998) Investigation of the thermal and morphological behavior of liquid-crystalline acetylene homo- and copolymers. Macromolecules 31(26):9166–9173

    Article  CAS  Google Scholar 

  • Kong X, Tang BZ (1998) Synthesis and novel mesomorphic properties of the side-chain liquid crystalline polyacetylenes containing phenyl benzoate mesogens with cyano and methoxy tails. Chem Mater 10:3352–3363

    Article  CAS  Google Scholar 

  • Kwak G, Minakuchi M, Sakaguchi T, Masuda T, Fujiki M (2007) Poly(diphenylacetylene) bearing long alkyl side chain via silylene linkage: its lyotropic liquid crystallinity and optical anisotropy. Chem Mater 19:3654–3661

    Article  CAS  Google Scholar 

  • Kwak G, Minakuchi M, Sakaguchi T, Masuda T, Fujiki M (2008) Alkyl side-chain length effects on fluorescence dynamics, lamellar layer structures, and optical anisotropy of poly(diphenylacetylene) derivatives. Macromolecules 41:2743–2746

    Article  CAS  Google Scholar 

  • Liu J, Lam JWY, Tang BZ (2009a) Acetylenic polymers: syntheses, structures, and functions. Chem Rev 109:5799–5867

    Article  CAS  PubMed  Google Scholar 

  • Liu KP, Yu ZQ, Liu JH, Chen EQ (2009b) Molecular shapes of monosubstituted polyacetylenes in their liquid crystalline phases. Macromol Chem Phys 210:707–716

    Article  CAS  Google Scholar 

  • Masuda T, Iguchi Y, Tang BZ, Higashimura T (1988) Diffusion and solution of gases in substituted polyacetylene membranes. Polymer 29:2041–2049

    Article  CAS  Google Scholar 

  • Moigne JL, Hilberer A, Kajzar F (1992) Polyacetylenes with cholesteryl side-groups: synthesis, linear and non-linear optical properties of soluble conjugated polymers. Makromol Chem 193:515–530

    Article  Google Scholar 

  • Mullen K, Reynolds JR, Masuda T (eds) (2014) Conjugated polymers: a practical guide to synthesis. RSC, Cambridge

    Google Scholar 

  • Naarrmann H, Theophilou N (1987) New process for the production of metal-like stable polyacetylene. Synth Met 22:1–8

    Article  Google Scholar 

  • Oh SY, Akagi K, Shirakawa H (1993) Synthesis and properties of liquid-crystalline polyacetylenes with a phenylcyclohexyl mesogenic moiety in the side group. Macromolecules 26:6203–6206

    Article  CAS  Google Scholar 

  • Okoshi K, Sakajiri K, Kumaki J, Yashima E (2005) Well-defined lyotropic liquid crystalline properties of rigid-rod helical polyacetylenes. Macromolecules 38:4061–4064

    Article  CAS  Google Scholar 

  • Peng H, Chen Y, Chen J, He X, Li F (2010) Luminescent mesogen jacketed poly(1-alkyne) bearing lateral terphenyl with hexyloxy tail. J Polym Sci A Polym Chem 48:5679–5692

    Article  CAS  Google Scholar 

  • Perepichka IF, Perepichka DF (eds) (2009) Handbook of thiophene-based materials: applications in organic electronics and photonics. Wiley, New York

    Google Scholar 

  • Sakaguchi T, Yumoto K, Shiotsuki M, Sanda F, Yoshikawa M, Masuda T (2008) Synthesis of poly(diphenylacetylene) membranes by desilylation of various precursor polymers and their properties. Macromolecules 38:2704–2709

    Article  Google Scholar 

  • San Jose BA, Matsushita S, Moroishi Y, Akagi K (2011) Disubstituted liquid crystalline polyacetylene derivatives that exhibit linearly polarized blue and green emissions. Macromolecules 44:6288–6263

    Article  CAS  Google Scholar 

  • Shibaev VP, Lam L (eds) (1994) Liquid crystalline and mesomorphic polymers. Springer, New York

    Google Scholar 

  • Shiotsuki M, Sanda F, Masuda T (2011) Polymerization of substituted acetylenes and features of the formed polymers. Polym Chem 2:1044–1058

    Article  CAS  Google Scholar 

  • Shukla A, Mazumdar S (1999) Designing emissive conjugated polymers with small optical gaps: a step towards organic polymeric infrared lasers. Phys Rev Lett 83:3944–3947

    Article  CAS  Google Scholar 

  • Shukla A, Ghosh H, Mazumdar S (2001) Photophysics of phenyl-substituted polyacetylenes, theory. Synth Met 116:87–90

    Article  CAS  Google Scholar 

  • Skotheim TA, Reynolds JR (eds) (2007) Handbook of conducting polymers, conjugated polymers: theory, synthesis, properties, and characterization. CRC Press, New York

    Google Scholar 

  • Suda K, Akagi K (2008) Electro-optical behavior of ferroelectric liquid crystalline polyphenylene derivatives. J Polym Sci A Polym Chem 46:3591–3610

    Article  CAS  Google Scholar 

  • Ting CH, Chen JT, Hsu CS (2002) Synthesis and thermal and photoluminescence properties of liquid crystalline polyacetylenes containing 4-alkanyloxyphenyl trans-4-alkylcyclohexanoate side groups. Macromolecules 35:1180–1189

    Article  CAS  Google Scholar 

  • Tsukamoto J, Takahashi A, Kawasaki K (1990) Structure and electrical properties of polyacetylene yielding a conductivity of 105 S/cm. Jpn J Appl Phys 29:125–130

    Article  CAS  Google Scholar 

  • Vicentini F, Mauzac M, Laversanne R, Pochat P, Parneix JP (1994) Coupling order and conductivity. Liquid crystalline conjugated polymers. Liq Cryst 16:721–733

    Article  CAS  Google Scholar 

  • Yu ZQ, Lam JWY, Zhao K, Zhu CZ, Yuang S, Lin JS, Li BS, Liu JH, Chen EQ, Tang BZ (2013) Mesogen jacketed liquid crystalline polyacetylene containing triphenylene discogen: synthesis and phase structure. Polym Chem 4:996–1005

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The author is grateful to Dr. Benedict A. San Jose and Dr. Satoshi Matsushita (Department of Polymer Chemistry, Kyoto University) for their valuable contributions in the syntheses of liquid crystalline conjugated polymers. This work was supported by a Grant-in-Aid for Science Research (A) (No. 25246002) and (No. 25620098) and (No. 15K13706) from the Ministry of Education, Culture, Sports, Science and Technology, Japan.

Author information

Authors and Affiliations

  1. Research Organization of Science and Technology, Ritsumeikan University, Kusatsu, Japan

    Kazuo Akagi

Authors
  1. Kazuo Akagi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Kazuo Akagi .

Editor information

Editors and Affiliations

  1. Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, OH, USA

    Lei Zhu

  2. Department of Materials Science and Engineering, Drexel University, Philadelphia, PA, USA

    Christopher Y. Li

Rights and permissions

Reprints and permissions

Copyright information

© 2020 Springer Nature Switzerland AG

About this entry

Check for updates. Verify currency and authenticity via CrossMark

Cite this entry

Akagi, K. (2020). Liquid Crystalline Conjugated Polymers with Optoelectronic Functions. In: Zhu, L., Li, C. (eds) Liquid Crystalline Polymers. Polymers and Polymeric Composites: A Reference Series. Springer, Cham. https://doi.org/10.1007/978-3-030-43350-5_46

Download citation

Publish with us

Policies and ethics

Search

Navigation