Rubbing-induced molecular reorientation on an alignment surface of an aromatic polyimide containing cyanobiphenyl side chains

J. J. Ge, C. Y. Li, G. Xue, I. K. Mann, D. Zhang, S. Y. Wang, F. W. Harris, S. Z D Cheng, Seok Cheol Hong, X. Zhuang, Y. R. Shen

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Abstract

Surface lamellar decoration (SLD), surface enhanced Raman scattering (SERS) and optical second harmonic generation (SHG) experiments have been utilized to study the molecular orientation and conformation changes at a rubbed polyimide alignment-layer surface. This aromatic polyimide containing pendent cyanobiphenyl mesogens was synthesized via a polycondensation of 2,2′-bis(3,4-dicarboxy-phenyl)hexafluoropropane dianhydride (6FDA) with bis{ω-[4-(4-cyanophenyl)phenoxy]hexyl} 4,4′-diamino-2,2′-biphenyldicarboxylate (nCBBP, n = 6), abbreviated as 6FDA-6CBBP. Uniform alignment layers, possessing high pretilt angles ranging from 39° to 43°, have been achieved after mechanical rubbing of the polyimide thin film surface at room temperature and subsequent annealing. This is the first time that high pretilt angles have been detected to possess a negative angle (-θc) with respect to the rubbing direction (i.e., opposite to the rubbing direction), considerably different from the conventional pretilt angle (θc) observed along the rubbing direction. This observation is confirmed using magnetic null and SHG methods. Combined polyethylene (PE) SLD and atomic force microscopy experiments reveal that the azimuthal orientation distribution of the long axis of the edge-on PE lamellar crystals is oriented normal to the rubbing direction, indicating that the PE chains are aligned parallel to the rubbing direction. This SLD technique probes the anisotropic surface orientation of the outermost molecules of the rubbed polyimide layer. The SERS results show that prior to rubbing the surface, both the pendent cyanobiphenyls in the side chains and backbones possess nearly planar chain conformations at the polyimide surface. Mechanical rubbing causes not only tilting of the backbone moieties, such as imide-phenylene structure, but also significant conformational rearrangements of the pendent side chains at the surfaces. The molecular mechanism of this unusual alignment is due to the fact that the pendent cyanobiphenyls forms a uniformly tilted conformation on the rubbed surface, and the polar cyano groups point down toward the layer surface deduced from SHG phase measurements. This conformational rearrangement of the side chains results in the formation of fold-like bent structures on the surface, which directly leads to the long axis of cyanobiphenyls having the -θc pretilt angle with respect to the rubbing direction.

Original languageEnglish
Pages (from-to)5768-5776
Number of pages9
JournalJournal of the American Chemical Society
Volume123
Issue number24
DOIs
Publication statusPublished - 2001 Oct 9
Externally publishedYes

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Polyimides
Polyethylene
Raman Spectrum Analysis
Imides
Molecular Conformation
Harmonic generation
Atomic Force Microscopy
Conformations
Polyethylenes
Direction compound
Raman scattering
Temperature
Point groups
Phase measurement
Molecular orientation
Polycondensation
Atomic force microscopy
Experiments
Annealing

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Rubbing-induced molecular reorientation on an alignment surface of an aromatic polyimide containing cyanobiphenyl side chains. / Ge, J. J.; Li, C. Y.; Xue, G.; Mann, I. K.; Zhang, D.; Wang, S. Y.; Harris, F. W.; Cheng, S. Z D; Hong, Seok Cheol; Zhuang, X.; Shen, Y. R.

In: Journal of the American Chemical Society, Vol. 123, No. 24, 09.10.2001, p. 5768-5776.

Research output: Contribution to journalArticle

Ge, JJ, Li, CY, Xue, G, Mann, IK, Zhang, D, Wang, SY, Harris, FW, Cheng, SZD, Hong, SC, Zhuang, X & Shen, YR 2001, 'Rubbing-induced molecular reorientation on an alignment surface of an aromatic polyimide containing cyanobiphenyl side chains', Journal of the American Chemical Society, vol. 123, no. 24, pp. 5768-5776. https://doi.org/10.1021/ja0042682
Ge, J. J. ; Li, C. Y. ; Xue, G. ; Mann, I. K. ; Zhang, D. ; Wang, S. Y. ; Harris, F. W. ; Cheng, S. Z D ; Hong, Seok Cheol ; Zhuang, X. ; Shen, Y. R. / Rubbing-induced molecular reorientation on an alignment surface of an aromatic polyimide containing cyanobiphenyl side chains. In: Journal of the American Chemical Society. 2001 ; Vol. 123, No. 24. pp. 5768-5776.
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abstract = "Surface lamellar decoration (SLD), surface enhanced Raman scattering (SERS) and optical second harmonic generation (SHG) experiments have been utilized to study the molecular orientation and conformation changes at a rubbed polyimide alignment-layer surface. This aromatic polyimide containing pendent cyanobiphenyl mesogens was synthesized via a polycondensation of 2,2′-bis(3,4-dicarboxy-phenyl)hexafluoropropane dianhydride (6FDA) with bis{ω-[4-(4-cyanophenyl)phenoxy]hexyl} 4,4′-diamino-2,2′-biphenyldicarboxylate (nCBBP, n = 6), abbreviated as 6FDA-6CBBP. Uniform alignment layers, possessing high pretilt angles ranging from 39° to 43°, have been achieved after mechanical rubbing of the polyimide thin film surface at room temperature and subsequent annealing. This is the first time that high pretilt angles have been detected to possess a negative angle (-θc) with respect to the rubbing direction (i.e., opposite to the rubbing direction), considerably different from the conventional pretilt angle (θc) observed along the rubbing direction. This observation is confirmed using magnetic null and SHG methods. Combined polyethylene (PE) SLD and atomic force microscopy experiments reveal that the azimuthal orientation distribution of the long axis of the edge-on PE lamellar crystals is oriented normal to the rubbing direction, indicating that the PE chains are aligned parallel to the rubbing direction. This SLD technique probes the anisotropic surface orientation of the outermost molecules of the rubbed polyimide layer. The SERS results show that prior to rubbing the surface, both the pendent cyanobiphenyls in the side chains and backbones possess nearly planar chain conformations at the polyimide surface. Mechanical rubbing causes not only tilting of the backbone moieties, such as imide-phenylene structure, but also significant conformational rearrangements of the pendent side chains at the surfaces. The molecular mechanism of this unusual alignment is due to the fact that the pendent cyanobiphenyls forms a uniformly tilted conformation on the rubbed surface, and the polar cyano groups point down toward the layer surface deduced from SHG phase measurements. This conformational rearrangement of the side chains results in the formation of fold-like bent structures on the surface, which directly leads to the long axis of cyanobiphenyls having the -θc pretilt angle with respect to the rubbing direction.",
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T1 - Rubbing-induced molecular reorientation on an alignment surface of an aromatic polyimide containing cyanobiphenyl side chains

AU - Ge, J. J.

AU - Li, C. Y.

AU - Xue, G.

AU - Mann, I. K.

AU - Zhang, D.

AU - Wang, S. Y.

AU - Harris, F. W.

AU - Cheng, S. Z D

AU - Hong, Seok Cheol

AU - Zhuang, X.

AU - Shen, Y. R.

PY - 2001/10/9

Y1 - 2001/10/9

N2 - Surface lamellar decoration (SLD), surface enhanced Raman scattering (SERS) and optical second harmonic generation (SHG) experiments have been utilized to study the molecular orientation and conformation changes at a rubbed polyimide alignment-layer surface. This aromatic polyimide containing pendent cyanobiphenyl mesogens was synthesized via a polycondensation of 2,2′-bis(3,4-dicarboxy-phenyl)hexafluoropropane dianhydride (6FDA) with bis{ω-[4-(4-cyanophenyl)phenoxy]hexyl} 4,4′-diamino-2,2′-biphenyldicarboxylate (nCBBP, n = 6), abbreviated as 6FDA-6CBBP. Uniform alignment layers, possessing high pretilt angles ranging from 39° to 43°, have been achieved after mechanical rubbing of the polyimide thin film surface at room temperature and subsequent annealing. This is the first time that high pretilt angles have been detected to possess a negative angle (-θc) with respect to the rubbing direction (i.e., opposite to the rubbing direction), considerably different from the conventional pretilt angle (θc) observed along the rubbing direction. This observation is confirmed using magnetic null and SHG methods. Combined polyethylene (PE) SLD and atomic force microscopy experiments reveal that the azimuthal orientation distribution of the long axis of the edge-on PE lamellar crystals is oriented normal to the rubbing direction, indicating that the PE chains are aligned parallel to the rubbing direction. This SLD technique probes the anisotropic surface orientation of the outermost molecules of the rubbed polyimide layer. The SERS results show that prior to rubbing the surface, both the pendent cyanobiphenyls in the side chains and backbones possess nearly planar chain conformations at the polyimide surface. Mechanical rubbing causes not only tilting of the backbone moieties, such as imide-phenylene structure, but also significant conformational rearrangements of the pendent side chains at the surfaces. The molecular mechanism of this unusual alignment is due to the fact that the pendent cyanobiphenyls forms a uniformly tilted conformation on the rubbed surface, and the polar cyano groups point down toward the layer surface deduced from SHG phase measurements. This conformational rearrangement of the side chains results in the formation of fold-like bent structures on the surface, which directly leads to the long axis of cyanobiphenyls having the -θc pretilt angle with respect to the rubbing direction.

AB - Surface lamellar decoration (SLD), surface enhanced Raman scattering (SERS) and optical second harmonic generation (SHG) experiments have been utilized to study the molecular orientation and conformation changes at a rubbed polyimide alignment-layer surface. This aromatic polyimide containing pendent cyanobiphenyl mesogens was synthesized via a polycondensation of 2,2′-bis(3,4-dicarboxy-phenyl)hexafluoropropane dianhydride (6FDA) with bis{ω-[4-(4-cyanophenyl)phenoxy]hexyl} 4,4′-diamino-2,2′-biphenyldicarboxylate (nCBBP, n = 6), abbreviated as 6FDA-6CBBP. Uniform alignment layers, possessing high pretilt angles ranging from 39° to 43°, have been achieved after mechanical rubbing of the polyimide thin film surface at room temperature and subsequent annealing. This is the first time that high pretilt angles have been detected to possess a negative angle (-θc) with respect to the rubbing direction (i.e., opposite to the rubbing direction), considerably different from the conventional pretilt angle (θc) observed along the rubbing direction. This observation is confirmed using magnetic null and SHG methods. Combined polyethylene (PE) SLD and atomic force microscopy experiments reveal that the azimuthal orientation distribution of the long axis of the edge-on PE lamellar crystals is oriented normal to the rubbing direction, indicating that the PE chains are aligned parallel to the rubbing direction. This SLD technique probes the anisotropic surface orientation of the outermost molecules of the rubbed polyimide layer. The SERS results show that prior to rubbing the surface, both the pendent cyanobiphenyls in the side chains and backbones possess nearly planar chain conformations at the polyimide surface. Mechanical rubbing causes not only tilting of the backbone moieties, such as imide-phenylene structure, but also significant conformational rearrangements of the pendent side chains at the surfaces. The molecular mechanism of this unusual alignment is due to the fact that the pendent cyanobiphenyls forms a uniformly tilted conformation on the rubbed surface, and the polar cyano groups point down toward the layer surface deduced from SHG phase measurements. This conformational rearrangement of the side chains results in the formation of fold-like bent structures on the surface, which directly leads to the long axis of cyanobiphenyls having the -θc pretilt angle with respect to the rubbing direction.

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