Skip to main content
SpringerLink
Log in
Book cover

Polymers and Polymeric Composites: A Reference Series pp 1–32Cite as

Supramolecular Self-assembly of Discotic Liquid Crystalline LEGOs

  • Living reference work entry
  • First Online:

  • 136 Accesses

Abstract

Discotic liquid crystals with well-defined columnar self-assemblies are promising for technological applications in organic electronics such as organic solar cells and field-effect transistors. In this entry, we review the self-assembly behavior of discotic supermolecules comprised of various discotic and cubic building blocks, including porphyrin, phthalocyanine, triphenylene, and polyhedral oligomeric silsesquioxane (POSS). With the help of amide hydrogen bonding, triphenylenes and porphyrins stack into the ordered “lamello-columnar” phase. Without hydrogen bonding interaction, the π-π stacking interaction leads to a hexagonal columnar phase with mixed phthalocyanine and triphenylene columns. For a POSS molecule covalently attached to eight triphenylenes, the triphenylenes and the POSS core can form a super-column when the space length is short. Self-assembly of these supercolumns can lead to a hexagonal superlattice. From this study, the spacer length, molecular geometry/size, and intermolecular interactions play an important role in the self-assembly of the discotic liquid crystalline LEGOs.

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

References

  • Adam D, Schuhmacher P, Simmerer J, Haussling L, Siemensmeyer K, Etzbach KH, Ringsdorf H, Haarer D (1994) Fast photoconduction in the highly ordered columnar phase of a discotic liquid-crystal. Nature 371(6493):141–143

    Article  CAS  Google Scholar 

  • Bacher A, Bleyl I, Erdelen CH (1997) Low molecular weight and polymeric triphenylenes as hole transport materials inorganic two-layer LEDs. Adv Mater 9(13):1031–1035

    Article  CAS  Google Scholar 

  • Beginn U (2003) Thermotropic columnar mesophases from N-H·· O, and N···H-O hydrogen bond supramolecular mesogenes. Prog Polym Sci 28(7):1049–1105

    Article  CAS  Google Scholar 

  • Benanti TL, Saejueng P, Venkataraman D (2007) Segregated assemblies in bridged electron-rich and electron-poor π-conjugated moieties. Chem Commun (7):692–694

    Google Scholar 

  • Bu LJ, Guo XY, Yu B, Qu Y, Xie ZY, Yan DH, Geng YH, Wang FS (2009) Monodisperse co-oligomer approach toward nanostructured films with alternating donor-acceptor lamellae. J Am Chem Soc 131(37):13242–13243

    Article  CAS  Google Scholar 

  • Bullock JE, Carmieli R, Mickley SM, Vura-Weis J, Wasielewski MR (2009) Photoinitiated charge transport through π-stacked electron conduits in supramolecular ordered assemblies of donor-acceptor triads. J Am Chem Soc 131(33):11919–11929

    Article  CAS  Google Scholar 

  • Bushey ML, Hwang A, Stephens PW, Nuckolls C (2001) Enforced stacking in crowded arenes. J Am Chem Soc 123(33):8157–8158

    Article  CAS  Google Scholar 

  • Bushey ML, Hwang A, Stephens PW, Nuckolls C (2002) The consequences of chirality in crowded arenes – macromolecular helicity, hierarchical ordering, and directed assembly. Angew Chem Int Ed 41(15):2828–2831

    Article  CAS  Google Scholar 

  • Charvet R, Yamamoto Y, Sasaki T, Kim J, Kato K, Takata M, Saeki A, Seki S, Aida T (2012) Segregated and alternately stacked donor/acceptor nanodomains in tubular morphology tailored with zinc porphyrin-C60 amphiphilic dyads: clear geometrical effects on photoconduction. J Am Chem Soc 134(5):2524–2527

    Article  CAS  Google Scholar 

  • Christ T, Glusen B, Greiner A, Kettner A, Sander R, Stumpflen V, Tsukruk V, Wendorff JH (1997) Columnar discotics for light emitting diodes. Adv Mater 9(1):48–52

    Article  CAS  Google Scholar 

  • Cooke G, Kaushal N, Boden N, Bushby RJ, Lu ZB, Lozman O (2000) Synthesis of liquid crystalline anthraquinolyl-triphenylenes. Tetrahedron Lett 41(41):7955–7959

    Article  CAS  Google Scholar 

  • Dong L, Li W, Li WS (2011) Construction of a long range p/n heterojunction with a pair of nanometre-wide continuous D/A phases. Nanoscale 3(9):3447–3461

    Article  CAS  Google Scholar 

  • Dossel LF, Kamm V, Howard IA, Laquai F, Pisula W, Feng XL, Li C, Takase M, Kudernac T, De Feyter S, Mullen K (2012) Synthesis and controlled self-assembly of covalently linked hexa-peri-hexabenzocoronene/perylene diimide dyads as models to study fundamental energy and electron transfer processes. J Am Chem Soc 134(13):5876–5886

    Article  Google Scholar 

  • Gearba RI, Lehmann M, Levin J, Ivanov DA, Koch MHJ, Barbera J, Debije MG, Piris J, Geerts YH (2003) Tailoring discotic mesophases: columnar order enforced with hydrogen bonds. Adv Mater 15(19):1614–1618

    Article  CAS  Google Scholar 

  • Gommans H, Schols S, Kadashchuk A, Heremans P, Meskers SCJ (2009) Exciton diffusion length and lifetime in subphthalocyanine films. J Phys Chem C 113(7):2974–2979

    Article  CAS  Google Scholar 

  • Hanabusa K, Koto C, Kimura M, Shirai H, Kakehi A (1997) Remarkable viscoelasticity of organic solvents containing trialkyl-1,3,5-benzenetricarboxamides and their intermolecular hydrogen bonding. Chem Lett (5):429–430

    Article  Google Scholar 

  • Hayashi H, Nihashi W, Umeyama T, Matano Y, Seki S, Shimizu Y, Imahori H (2011) Segregated donor-acceptor columns in liquid crystals that exhibit highly efficient ambipolar charge transport. J Am Chem Soc 133(28):10736–10739

    Article  CAS  Google Scholar 

  • Hertmanowski R, Martynski T, Stolarski R, Bauman D (2008) Intermolecular interactions in Langmuir-Blodgett films of liquid crystalline perylene derivatives. Opto-Electron Rev 16(3):237–243

    Article  CAS  Google Scholar 

  • Hizume Y, Tashiro K, Charvet R, Yamamoto Y, Saeki A, Seki S, Aida T (2010) Chiroselective assembly of a chiral porphyrin-fullerene dyad: photoconductive nanofiber with a top-class ambipolar charge-carrier mobility. J Am Chem Soc 132(19):6628–6629

    Article  CAS  Google Scholar 

  • Hoeben FJM, Jonkheijm P, Meijer EW, Schenning APHJ (2005) About supramolecular assemblies of π-conjugated systems. Chem Rev 105(4):1491–1546

    Article  CAS  Google Scholar 

  • Ichihara M, Suzuki A, Hatsusaka K, Ohta K (2007) Discotic liquid crystals of transition metal complexes 38: peripheral chain substituent position effect on columnar mesophase and stacking structures of novel phthalocyanine-based liquid crystals. J Porphyrins Phthalocyanines 11(7):503–512

    Article  CAS  Google Scholar 

  • Ito S, Wehmeier M, Brand JD, Kubel C, Epsch R, Rabe JP, Mullen K (2000) Synthesis and self-assembly of functionalized hexa-peri-hexabenzocoronenes. Chem Eur J 6(23):4327–4342

    Article  CAS  Google Scholar 

  • Janietz D (1998) Structure formation of functional sheet-shaped mesogens. J Mater Chem 8(2):265–274

    Article  CAS  Google Scholar 

  • Kawada H, Matsunaga Y, Takamura T, Terada M (1988) Design of novel mesomorphic compounds methyl-substituted N,N′-dialkanoyl-1,3-benzenediamines. Can J Chem 66(8):1867–1871

    Article  CAS  Google Scholar 

  • Kumar S, Rao DSS, Prasad SK (1999) New branched chain tricycloquinazoline derivatives: a room temperature electron deficient discotic system. J Mater Chem 9(11):2751–2754

    Article  CAS  Google Scholar 

  • Laschat S, Baro A, Steinke N, Giesselmann F, Hagele C, Scalia G, Judele R, Kapatsina E, Sauer S, Schreivogel A, Tosoni M (2007) Discotic liquid crystals: from tailor-made synthesis to plastic electronics. Angew Chem Int Ed 46(26):4832–4887

    Article  CAS  Google Scholar 

  • Li WS, Yamamoto Y, Fukushima T, Saeki A, Seki S, Tagawa S, Masunaga H, Sasaki S, Takata M, Aida T (2008) Amphiphilic molecular design as a rational strategy for tailoring bicontinuous electron donor and acceptor arrays: photoconductive liquid crystalline oligothiophene-C60 dyads. J Am Chem Soc 130(28):8886–8887

    Article  CAS  Google Scholar 

  • Liu CY, Bard AJ (2002) Pressure-induced insulator-conductor transition in a photoconducting organic liquid-crystal film. Nature 418(6894):162–164

    Article  CAS  Google Scholar 

  • Mahlstedt S, Janietz D, Stracke A, Wendorff JH (2000) First triphenylene based non-symmetric donor-acceptor triple mesogen possessing disc-like and rod-like characteristics. Chem Commun (1):15–16

    Google Scholar 

  • Mativetsky JM, Kastler M, Savage RC, Gentilini D, Palma M, Pisula W, Mullen K, Samori P (2009) Self-assembly of a donor-acceptor dyad across multiple length scales: functional architectures for organic electronics. Adv Funct Mater 19(15):2486–2494

    Article  CAS  Google Scholar 

  • Meier H (1992) The photochemistry of stilbenoid compounds and their role in materials technology. Angew Chem Int Ed 31(11):1399–1420

    Article  Google Scholar 

  • Miao J, Zhu L (2010a) Columnar liquid crystalline assembly of doubly discotic supermolecules based on tetra-triphenylene-substituted phthalocyanine. Soft Matter 6(9):2072–2079

    Article  CAS  Google Scholar 

  • Miao J, Zhu L (2010b) Hydrogen bonding induced supramolecular self-assembly of linear doubly discotic triad supermolecules. Chem Asian J 5(7):1634–1641

    Article  CAS  Google Scholar 

  • Miao J, Zhu L (2010c) Hydrogen bond-assisted supramolecular self-assembly of doubly discotic supermolecules based on porphyrin and triphenylene. Chem Mater 22(1):197–206

    Article  CAS  Google Scholar 

  • Miao J, Zhu L (2010d) Topology controlled supramolecular self-assembly of octa triphenylene-substituted polyhedral oligomeric silsesquioxane hybrid supermolecules. J Phys Chem B 114(5):1879–1887

    Article  CAS  Google Scholar 

  • Nelson J (2001) Solar energy – solar cells by self-assembly? Science 293(5532):1059–1060

    Article  CAS  Google Scholar 

  • Oukachmih M, Destruel P, Seguy I, Ablart G, Jolinat P, Archambeau S, Mabiala M, Fouet S, Bock H (2005) New organic discotic materials for photovoltaic conversion. Sol Energy Mater Sol Cells 85(4):535–543

    Article  CAS  Google Scholar 

  • Palmans ARA, Vekemans JAJM, Havinga EE, Meijer EW (1997) Sergeants-and-soldiers principle in chiral columnar stacks of disc-shaped molecules with C3 symmetry. Angew Chem Int Ed 36(23):2648–2651

    Article  CAS  Google Scholar 

  • Paraschiv I, Giesbers M, van Lagen B, Grozema FC, Abellon RD, Siebbeles LDA, Marcelis ATM, Zuilhof H, Sudholter EJR (2006) H-bond-stabilized triphenylene-based columnar discotic liquid crystals. Chem Mater 18(4):968–974

    Article  CAS  Google Scholar 

  • Paraschiv I, de Lange K, Giesbers M, van Lagen B, Grozema FC, Abellon RD, Siebbeles LDA, Sudholter EJR, Zuilhof H, Marcelis ATM (2008) Hydrogen-bond stabilized columnar discotic benzenetrisamides with pendant triphenylene groups. J Mater Chem 18(45):5475–5481

    Article  CAS  Google Scholar 

  • Peeters E, van Hal PA, Meskers SCJ, Janssen RAJ, Meijer EW (2002) Photoinduced electron transfer in a mesogenic donor-acceptor-donor system. Chem Eur J 8(19):4470–4474

    Article  CAS  Google Scholar 

  • Pieterse K, van Hal PA, Kleppinger R, Vekemans JAJM, Janssen RAJ, Meijer EW (2001) An electron-deficient discotic liquid-crystalline material. Chem Mater 13(8):2675–2679

    Article  CAS  Google Scholar 

  • Pisula W, Menon A, Stepputat M, Lieberwirth I, Kolb U, Tracz A, Sirringhaus H, Pakula T, Mullen K (2005) A zone-casting technique for device fabrication of field-effect transistors based on discotic hexa-peri-hexabenzocoronene. Adv Mater 17(6):684–689

    Article  CAS  Google Scholar 

  • Saleh M, Park YS, Baumgarten M, Kim JJ, Mullen K (2009) Conjugated triphenylene polymers for blue OLED devices. Macromol Rapid Commun 30(14):1279–1283

    Article  CAS  Google Scholar 

  • Samori P, Fechtenkotter A, Reuther E, Watson MD, Severin N, Mullen K, Rabe JP (2006) Self-assembly of perylene monoimide substituted hexa-peri-bexabenzocoronenes: dyads and triads at surfaces. Adv Mater 18(10):1317–1321

    Article  CAS  Google Scholar 

  • Schmidt-Mende L, Fechtenkotter A, Mullen K, Moons E, Friend RH, MacKenzie JD (2001) Self-organized discotic liquid crystals for high-efficiency organic photovoltaics. Science 293(5532):1119–1122

    Article  CAS  Google Scholar 

  • Schultz A, Laschat S, Abbott AP, Langner M, Reeve TB (2000) Synthesis of novel donor-acceptor twins. J Chem Soc Perkin Trans 1(20):3356–3361

    Article  Google Scholar 

  • Seguy I, Destruel P, Bock H (2000) An all-columnar bilayer light-emitting diode. Synth Met 111:15–18

    Article  Google Scholar 

  • Sergeyev S, Pisula W, Geerts YH (2007) Discotic liquid crystals: a new generation of organic semiconductors. Chem Soc Rev 36(12):1902–1929

    Article  CAS  Google Scholar 

  • Simpson CD, Wu JS, Watson MD, Mullen K (2004) From graphite molecules to columnar superstructures – an exercise in nanoscience. J Mater Chem 14(4):494–504

    Article  CAS  Google Scholar 

  • Smulders MMJ, Schenning APHJ, Meijer EW (2008) Insight into the mechanisms of cooperative self-assembly: the “sergeants-and-soldiers” principle of chiral and achiral C3-symmetrical discotic triamides. J Am Chem Soc 130(2):606–611

    Article  CAS  Google Scholar 

  • Tchebotareva N, Yin XM, Watson MD, Samori P, Rabe JP, Mullen K (2003) Ordered architectures of a soluble hexa-peri-hexabenzocoronene-pyrene dyad: thermotropic bulk properties and nanoscale phase segregation at surfaces. J Am Chem Soc 125(32):9734–9739

    Article  CAS  Google Scholar 

  • Terao Y, Sasabe H, Adachi C (2007) Correlation of hole mobility, exciton diffusion length, and solar cell characteristics in phthalocyanine/fullerene organic solar cells. Appl Phys Lett 90(10):103515

    Article  Google Scholar 

  • Tschierske C (2001) Non-conventional soft matter. Annu Rep Prog Chem Sect C 97:191–267

    Article  CAS  Google Scholar 

  • van de Craats AM, Warman JM (2001) The core-size effect on the mobility of charge in discotic liquid crystalline materials. Adv Mater 13(2):130–133

    Article  Google Scholar 

  • van de Craats AM, Warman JM, Hasebe H, Naito R, Ohta K (1997) Charge transport in the mesomorphic free-radical compound bis(octakis(dodecyloxy)phthalocyaninato)lutetium(III). J Phys Chem B 101(45):9224–9232

    Article  Google Scholar 

  • van de Craats AM, Warman JM, Mullen K, Geerts Y, Brand JD (1998) Rapid charge transport along self-assembling graphitic nanowires. Adv Mater 10(1):36–38

    Article  Google Scholar 

  • van de Craats AM, Warman JM, Fechtenkotter A, Brand JD, Harbison MA, Mullen K (1999) Record charge carrier mobility in a room-temperature discotic liquid-crystalline derivative of hexabenzocoronene. Adv Mater 11(17):1469–1472

    Article  Google Scholar 

  • van de Craats AM, Stutzmann N, Bunk O, Nielsen MM, Watson M, Mullen K, Chanzy HD, Sirringhaus H, Friend RH (2003) Meso-epitaxial solution-growth of self-organizing discotic liquid-crystalline semiconductors. Adv Mater 15(6):495–499

    Article  Google Scholar 

  • van Gorp JJ, Vekemans JAJM, Meijer EW (2002) C3-symmetrical supramolecular architectures: fibers and organic gels from discotic trisamides and trisureas. J Am Chem Soc 124(49):14759–14769

    Article  Google Scholar 

  • Wasserfallen D, Fischbach I, Chebotareva N, Kastler M, Pisula W, Jackel F, Watson MD, Schnell I, Rabe JP, Spiess HW, Mullen K (2005) Influence of hydrogen bonds on the supramolecular order of hexa-peri-hexabenzocoronenes. Adv Funct Mater 15(10):1585–1594

    Article  CAS  Google Scholar 

  • Zamir S, Poupko R, Luz Z, Huser B, Boeffel C, Zimmermann H (1994) Molecular ordering and dynamics in the columnar mesophase of a new dimeric discotic liquid-crystal as studied by X-ray-diffraction and deuterium NMR. J Am Chem Soc 116(5):1973–1980

    Article  CAS  Google Scholar 

  • Zeng DL, Tahar-Djebbar I, Xiao YM, Kameche F, Kayunkid N, Brinkmann M, Guillon D, Heinrich B, Donnio B, Ivanov DA, Lacaze E, Kreher D, Mathevet F, Attias AJ (2014) Intertwined lamello-columnar coassemblies in liquid-crystalline side-chain π-conjugated polymers: toward a new class of nanostructured supramolecular organic semiconductors. Macromolecules 47(5):1715–1731

    Article  CAS  Google Scholar 

  • Zhao KQ, An LL, Zhang XB, Yu WH, Hu P, Wang BQ, Xu J, Zeng QD, Monobe H, Shimizu Y, Heinrich B, Donnio B (2015) Highly segregated lamello-columnar mesophase organizations and fast charge carrier mobility in new discotic donor-acceptor triads. Chem Eur J 21(29):10379–10390

    Article  CAS  Google Scholar 

Download references

Acknowledgment

This work was supported by the National Science Foundation CAREER Award (DMR-0348724), DuPont Young Professor Award, and 3M Nontenured Faculty Award.

Author information

Authors and Affiliations

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

    Lei Zhu

Authors
  1. Lei Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Lei Zhu .

Editor information

Editors and Affiliations

  1. Indian Institute of Technology-Roorkee, Saharanpur, India

    Sanjay Palsule

Rights and permissions

Reprints and permissions

Copyright information

© 2018 Springer-Verlag GmbH Germany, part of Springer Nature

About this entry

Check for updates. Verify currency and authenticity via CrossMark

Cite this entry

Zhu, L. (2018). Supramolecular Self-assembly of Discotic Liquid Crystalline LEGOs. In: Palsule, S. (eds) Polymers and Polymeric Composites: A Reference Series. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-37179-0_65-1

Download citation

  • DOI: https://doi.org/10.1007/978-3-642-37179-0_65-1

  • Received:

  • Accepted:

  • Published:

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-642-37179-0

  • Online ISBN: 978-3-642-37179-0

  • eBook Packages: Springer Reference Chemistry and Mat. ScienceReference Module Physical and Materials ScienceReference Module Chemistry, Materials and Physics

Publish with us

Policies and ethics

Search

Navigation