Skip to main content
SpringerLink
Log in

Theoretical studies on organosilicon oligomers containing ethenylene moieties

  • Original Paper
  • Published:
Journal of Polymer Research Aims and scope Submit manuscript

Abstract

The geometric and electronic structures of organosilicon oligomers, nSi Lx (C=C)y with linear silicon segments and nSi Rx (C=C)y with cyclic silicon segments, are studied by using the density functional theory. It is found from the calculated results that the extension of the π-conjugation plays an important role in tuning the geometric and electronic structures. The band gap tends to be decreased and the hole injection rate tends to be increased with the elongation of the π-conjugated units. An effective σ-π conjugation occurs between the silanylene moiety and the ethenylene moiety, especially for the polymers with a rather small π-electron moiety. Interestingly, an even/odd effect of the band gap is found. A PSi Rx (C=C)y has narrower band gap than a corresponding PSi Lx (C=C)y. These results are in good agreement with the experimental observations.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Ohshita J, Kanaya D, Ishikawa M, Yamanaka T (1989) Polymeric organo-silicon systems. 6. Synthesis and properties of trans-poly[(disilanylene)ethenylene]. J Organomet Chem 369:C18–C20

    Article  CAS  Google Scholar 

  2. Iwahara T, Hayase S, West R (1990) Synthesis and properties of ethynylene-disilanylene copolymers. Macromolecules 23:1298–1301

    Article  CAS  Google Scholar 

  3. Ijadi-Maghsoodi S, Pang Y, Barton TJ (1990) Efficient, one-pot synthesis of silylene-acetylene and disilylene-acetylene preceramic polymers from trichloroethylene. J Polym Sci A Polym Chem 28:955–965

    Article  CAS  Google Scholar 

  4. Ishikawa M, Hatano T, Hasegawa Y, Horio T, Kunai A, Miyai Y, Ishida T, Tsukihara T, Yamanaka T, Koike T, Shioya J (1992) Polymeric organosilicon systems. 12. Synthesis and anionic ring-opening polymerization of 1,2,5,6-tetrasilacycloocta-3,7-diynes. Organometallics 11:1604–1618

    Article  CAS  Google Scholar 

  5. Ishikawa M, Horio T, Hatano T, Kunai A (1993) Polymeric organosilicon systems. 15. Thermal- and radical-induced polymerization of 1,2,5,6-tetrasilacycloocta-3,7-diynes. Organometallics 12:2078–2084

    Article  CAS  Google Scholar 

  6. Toyoda E, Kunai A, Ishikawa M (1995) Polymeric organosilicon systems. 24. Anionic polymerization of 4,5,10-Trisilabicyclo[6.3.0]undeca-1(11),8-diene-2,6-diynes. Organometallics 14:1089–1091

    Article  CAS  Google Scholar 

  7. Ishikawa M, Sakamoto H, Ishii M, Ohshita J (1993) Polymeric organosilicon systems. 17. Synthesis and photochemical and conducting properties of poly[o-(disiladylene)phenylene and m-(disilanylene)phenylene]s. J Polym Sci Polym Sci 31:3281–3289

    CAS  Google Scholar 

  8. Kira M, Tokura S (1997) Thermal ring-opening polymerization of [2.2]paracyclophanes having two disilanylene bridges. Organometallics 16:1100–1102

    Article  CAS  Google Scholar 

  9. Ohshita J, Uemura T, Inoue T, Hino K, Kunai A (2006) Preparation of poly(silylene-p-phenylene)s bearing a benzo crown pendant group and their iono- and solvatochromic behavior in the emission spectra. Organometallics 25:2225–2229

    Article  CAS  Google Scholar 

  10. Li Z, Iida K, Tomisaka Y, Yoshimura A, Hirao T, Nomoto A, Ogawa A (2007) New entry to the construction of Si–Si linkages: Sm/SmI2-induced efficient reductive coupling of organochlorosilanes. Organometallics 26:1212–1216

    Article  Google Scholar 

  11. Zhou X, Niu Y, Huang F, Liu MS, Jen AKY (2007) Highly efficient UV violet light-emitting polymers derived from fluorene and tetraphenylsilane derivatives: molecular design toward enhanced electroluminescent performance. Macromolecules 40:3015–3020

    Article  CAS  Google Scholar 

  12. Ohshita J, Kanaya D, Ishikawa M, Koike T, Yamanaka T (1991) Polymeric organosilicon systems. 10. Synthesis and conducting properties of poly[2,5-(disilanylene)thienylenes]. Macromolecules 24:2106–2107

    Article  CAS  Google Scholar 

  13. Chicart P, Corriu RJP, Moreau JJE, Garnier F, Yassar A (1991) Selective synthetic routes to electroconductive organosilicon polymers containing thiophene units. Chem Mater 3:8–10

    Article  CAS  Google Scholar 

  14. Chicart P, Corriu RJP, Moreau JJE, Garnier F, Yassar A (1992) In: Laine RH (ed) Inorganic and organometallic polymers with special properties. Kluwer, Dordrecht, p 179

    Google Scholar 

  15. Fang MC, Watanabe A, Matsuda M (1995) Synthesis of silylene-phenylene and silylene-thienylene copolymers and their optical-properties. J Organomet Chem 489:15–22

    Article  CAS  Google Scholar 

  16. Ohshita J, Kunai A (1998) Polymers with alternating organosilicon and pi-conjugated units. Acta Polym 49:379–403

    Article  CAS  Google Scholar 

  17. Uhlig W (2002) Synthesis, functionalization, and cross-linking reactions of organosilicon polymers using silyl triflate intermediates. Prog Polym Sci 27:255–305

    Article  CAS  Google Scholar 

  18. Ohshita J, Matsuguchi A, Fukumori K, Hong RF, Ishikawa M, Yamanaka T, Koike T, Shioya J (1992) Polymeric organosilicon systems. 11. Synthesis and some properties of poly(disilanylenebutenyne-1,4-diyls) and poly[(methylphenylsilylene)butenyne-1,4-diyl]. Macromolecules 25:2134–2140

    Article  CAS  Google Scholar 

  19. Ishikawa M, Sakamoto H, Ishii M, Ohshita J (1993) Polymeric organosilicon systems. 17. Synthesis and photochemical and conducting properties of poly[o-(disiladylene)phenylene and m-(disilanylene)phenylene]s. J Polym Sci A Polym Chem 31:3281–3289

    Article  CAS  Google Scholar 

  20. Ohshita J, Kanaya D, Ishikawa M (1993) Polymeric organosilicon systems. 14. Synthesis and some properties of alternating polymers composed of a dithienylene group and a mono-silanylene, di-silanylene or tri-silanylene unit. Appl Organomet Chem 7:269–277

    Article  CAS  Google Scholar 

  21. Ohshita J, Hashimoto M, Lee KH, Yoshida H, Kunai A (2003) Synthesis of organosilanylene-thienylene alternating oligomers bearing ether side chains. J Organomet Chem 682:267–271

    Article  CAS  Google Scholar 

  22. Ohshita J, Watanabe T, Kanaya D, Ohsaki H, Ishikawa M, Ago H, Tanaka K, Yamabe T (1994) Polymeric organosilicon systems. 22. Synthesis and photochemical properties of poly[(disilanylene)oligophenylylenes] and poly[(silylene)biphenylylenes]. Organometallics 13:5002–5012

    Article  CAS  Google Scholar 

  23. Fang M, Watanabe A, Matsuda M (1996) Emission spectra of σ-π conjugated organosilicon copolymers consisting of alternating dimethylsilylene and aromatic units. Macromolecules 29:6807–6813

    Article  CAS  Google Scholar 

  24. Ohshita J, Takata A, Kai H, Kunai A, Komaguchi K, Shiotani M, Adachi A, Sakamaki K, Okita K, Harima Y, Kunugi Y, Yamashita K, Ishikawa M (2000) Synthesis of polymers with alternating organosilanylene and oligothienylene units and their optical, conducting, and hole-transporting properties. Organometallics 19:4492–4498

    Article  CAS  Google Scholar 

  25. Tanaka K, Nakajima K, Okada M, Yamabe T, Ishikawa M (1991) Electronic structures of simplified polymeric organosilicon systems containing π-conjugated moieties. Organometallics 10:2679–2684

    Article  CAS  Google Scholar 

  26. Tanaka K, Nakajima K, Okada M, Yamabe T, Ishikawa M (1992) Influence of the π-conjugated carbon moiety on the electronic structure of polymeric organosilicon systems. Organometallics 11:3191–3195

    Article  CAS  Google Scholar 

  27. Tanaka K, Ago H, Yamabe T, Ishikawa M, Ueda T (1994) Electronic structures of organosilicon polymers containing thienylene units. Organometallics 13:3496–3501

    Article  CAS  Google Scholar 

  28. Maxka J, Teramae H (1999) Electronic structures of polymers containing carbon multiple bond and disilane units in their backbone. Macromolecules 32:7045–7050

    Article  CAS  Google Scholar 

  29. Brough LF, West R (1981) The permethylcyclosilanes (Me2Si)5 through (Me2Si)35. J Am Chem Soc 103:3049–3056

    Article  CAS  Google Scholar 

  30. Wagner H, Wallner A, Fischer J, Flock M, Baumgartner J, Marschner C (2007) Rearrangement of cyclic silanes with aluminum trichloride. Organometallics 26:6704–6717

    Article  CAS  Google Scholar 

  31. Hengge E, Janoschek R (1995) Homocyclic silanes. Chem Rev 95:1495–1526

    Article  CAS  Google Scholar 

  32. Shikawa M, Watanabe M, Iyoda J, Ikeda H, Kumada M (1982) Aluminum chloride catalyzed skeletal rearrangement of permethylated cyclic polysilanes. Organometallics 1:317–322

    Article  Google Scholar 

  33. Mitter FK, Pollhammer G, Hengge E (1986) Bicyclic silanes from cylosilane-metalderivatives. J Organomet Chem 314:1–5

    Article  CAS  Google Scholar 

  34. Hassler K, Mitter FK, Hengge E, Kratky C, Wagner UG (1987) Bond-elucidations for oligocyclic silanes. J Organomet Chem 333:291–303

    Article  CAS  Google Scholar 

  35. Mitter FK, Mitter FK, Hengge E (1987) Preparation of new polycyclic methyl silanes. J Organomet Chem 332:47–52

    Article  CAS  Google Scholar 

  36. Hengge E, Jenkner PKZ (1988) On the synthesis of permethylated alpha, omega-bis(cyclopentasilanyl)silanes. Anorg Allg Chem 560:27–34

    Article  CAS  Google Scholar 

  37. Zhang G, Ma J, Jiang Y (2005) Charge-doped and heteroatom-sbstituted polysilane, poly(vinylenedisilanylene), and poly(butadienylenedisilanylene): electronic structures and band gaps. J Phys Chem B 109:13499–13509

    Article  CAS  Google Scholar 

  38. Stueger H, Fuerpass G, Renger K, Baumgartner J (2005) Synthesis, structures, and unusual photoluminescence of O- and N-functional cyclohexasilanes. Organometallics 24:6374–6381

    Article  CAS  Google Scholar 

  39. Parr RG, Yang W (1989) Density-functional theory of atoms and molecules. Oxford University Press, New York

    Google Scholar 

  40. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA Jr, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2003) Gaussian 03, Revision B.04. Gaussian, Inc., Pittsburgh

    Google Scholar 

  41. Politzer P, Nurray JS (1996) In: Molecular electrostatic potentials: concepts and applications. Elsevier, Amsterdam, p 649

  42. Boris B, Petia B (1999) Molecular electrostatic potential as reactivity index in hydrogen bonding: Ab initio molecular orbital study of complexes of nitrile and carbonyl compounds with hydrogen fluoride. J Phys Chem A 103:6793–6799

    Article  Google Scholar 

  43. Gadre SR, Bhadane PK (1999) Molecular electrostatics for exploring complexes of carbonyl compounds and hydrogen fluoride. J Phys Chem A 103:3512–3517

    Article  CAS  Google Scholar 

  44. Laaksonen L (1992) A graphics program for the analysis and display of molecular-dynamics trajectories. J Mol Graph 10:33–34

    Article  CAS  Google Scholar 

  45. Sheldrick WS (1989) In: Patai S, Rappoport Z (eds) The chemistry of organic silicon compounds, chapter 3. Wiley, New York

    Google Scholar 

  46. Zhang G, Ma J, Jiang Y (2003) Effects of silole content and doping on the electronic structures and excitation energies of silole/thiophene cooligomers. Macromolecules 36:2130–2140

    Article  CAS  Google Scholar 

  47. Kunai A, Ueda T, Horata K, Toyoda E, Nagamoto I, Ohshita J, Ishikawa M, Tanaka K (1996) Polymeric organosilicon systems. 26. Synthesis and photochemical and conducting properties of poly[(tetraethyldisilanylene)oligo(2,5-thienylenes)]. Organometallics 15:2000–2008

    Article  CAS  Google Scholar 

  48. Chwang AB, Frisbie CD (2000) Field effect transport measurements on single grains of sexithiophene: role of the contacts. J Phys Chem B 104:12202–12209

    Article  CAS  Google Scholar 

  49. Mahapatro AK, Ghosh S (2002) Schottky energy barrier and charge injection in metal/copper-phthalocyanine/metal structures. Appl Phys Lett 80:4840–4842

    Article  CAS  Google Scholar 

  50. Ohshita J, Matsushige K, Kunai A, Adachi A, Sakamaki K, Okita K (2000) Synthesis and ring-opening reactions of 1,8-silanonaphthalenes. Organometallics 19:5582–5588

    Article  CAS  Google Scholar 

  51. Ohshita J, Yoshimoto K, Hashimoto M, Hamamoto D, Kunai A, Harima Y, Kunugi Y, Yamashita K, Kakimoto M, Ishikawa M (2003) Synthesis of organosilanylene-pentathienylene alternating polymers and their application to the hole-transporting materials in double-layer electroluminescent devices. J Organomet Chem 665:29–32

    Article  CAS  Google Scholar 

Download references

Acknowledgment

The authors thank three reviewers for their constructive and pertinent comments. The authors also thank the NSF of China (51073048), the SF for leaders in academe of Harbin City of China (2010RFJGG016), the Heilongjiang Postdoctoral Grant (LBHQ07058), the Special Foundation for Young Scientists of Heilongjiang Province (QC06025), the SF of jiaoyuting of Heilongjiang province of China (11541063), and the SF for elitists of Harbin University of Science and Technology.

Author information

Authors and Affiliations

  1. Key Laboratory of Green Chemical Technology of College of Heilongjiang Province, College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin, 150080, People’s Republic of China

    Yan Shang, LuQing Yang, GuiLing Zhang, Hui Zhang & Bo Liu

Authors
  1. Yan Shang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. LuQing Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. GuiLing Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Hui Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Bo Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to GuiLing Zhang.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(DOC 320 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Shang, Y., Yang, L., Zhang, G. et al. Theoretical studies on organosilicon oligomers containing ethenylene moieties. J Polym Res 18, 1889–1902 (2011). https://doi.org/10.1007/s10965-011-9596-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10965-011-9596-4

Keywords

Search

Navigation