Supramolecular approaches to second-order nonlinear optical materials. Self-assembly and microstructural characterization of intrinsically acentric [(aminophenyl)azo]pyridinium superlattices

Wenbin Lin, Weiping Lin, George K. Wong, Tobin J Marks

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Abstract

This paper describes the synthesis and characterization of self-assembled second-order nonlinear optical multilayer materials containing the high-hyperpolarizability [(aminophenyl)azo]pyridinium chromophore. The chromophoric multilayers are assembled on clean glass or single-crystal silicon substrates via the following iterative reaction sequence: (1) treatment with 4-ClCH2C6H4SiCl3, 3-BrC3H6SiCl3, or 3-IC3H6SiCl3 to afford a self-assembled coupling layer; (2) quaternization of 4-[[4-[N,N-bis(hydroxylethyl)amino]phenyl]azo]pyridine in a 'topotactic' fashion to generate an [(aminophenyl)azo]pyridinium chromophore layer; (3) cross-linking with octachlorotrisiloxane to afford a capping layer (which also regenerates surface hydroxyl groups for subsequent layer deposition). The new chromophore precursor 4-[[4-[N,N-bis(hydroxylethyl)-amino]phenyl]azo]pyridine was synthesized by diazotization of 4-aminopyridine followed by coupling with N-phenyldiethanolamine and has been characterized by elemental analysis, mass spectrometry, and infrared, UV-vis, and NMR spectroscopies. The chromophoric multilayers have been characterized by X-ray photoelectron and transmission optical spectroscopies, spectroscopic ellipsometry, X-ray reflectivity, advancing contact angle measurements, and polarized second harmonic generation (SHG). The excellent structural regularity of the chromophoric multilayers is indicated by the linear dependence of the [(aminophenyl)azo]pyridinium chromophore longitudinal HOMO → LUMO charge-transfer excitation absorbance at 572 nm and the ellipsometry- and X-ray reflectivity-derived multilayer thicknesses on the number of assembled trilayers, while the uniform polar order of the stacked chromophoric multilayers is evidenced by the quadratic dependence of the second hormonic generation intensities on the number of trilayers. The [(aminophenyl)azo]pyridinium multilayers are photochemically stable, have very high structural regularities, and exhibit a second-order nonlinear optical susceptibility (χ2((2))) of ~3.6 x 10-7 esu (~ 150 pm/V) at a fundamental wavelength of 1064 nm. Finally, atomic force microscopy reveals that the surfaces of the self-assembled multilayers are very smooth (root mean square roughness = 12 Å for a 10 trilayer sample), undoubtedly reflecting the high three-dimensional structural regularities of the individual layers.

Original languageEnglish
Pages (from-to)8034-8042
Number of pages9
JournalJournal of the American Chemical Society
Volume118
Issue number34
DOIs
Publication statusPublished - Aug 28 1996

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Optical materials
Superlattices
Self assembly
Multilayers
X-Rays
Chromophores
4-Aminopyridine
Atomic Force Microscopy
Silicon
Hydroxyl Radical
Glass
Mass Spectrometry
Spectrum Analysis
X rays
Pyridine
Magnetic Resonance Spectroscopy
Optical multilayers
Spectroscopic ellipsometry
Wave transmission
Ellipsometry

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{724c057ba93f48f991661cfdbc296f12,
title = "Supramolecular approaches to second-order nonlinear optical materials. Self-assembly and microstructural characterization of intrinsically acentric [(aminophenyl)azo]pyridinium superlattices",
abstract = "This paper describes the synthesis and characterization of self-assembled second-order nonlinear optical multilayer materials containing the high-hyperpolarizability [(aminophenyl)azo]pyridinium chromophore. The chromophoric multilayers are assembled on clean glass or single-crystal silicon substrates via the following iterative reaction sequence: (1) treatment with 4-ClCH2C6H4SiCl3, 3-BrC3H6SiCl3, or 3-IC3H6SiCl3 to afford a self-assembled coupling layer; (2) quaternization of 4-[[4-[N,N-bis(hydroxylethyl)amino]phenyl]azo]pyridine in a 'topotactic' fashion to generate an [(aminophenyl)azo]pyridinium chromophore layer; (3) cross-linking with octachlorotrisiloxane to afford a capping layer (which also regenerates surface hydroxyl groups for subsequent layer deposition). The new chromophore precursor 4-[[4-[N,N-bis(hydroxylethyl)-amino]phenyl]azo]pyridine was synthesized by diazotization of 4-aminopyridine followed by coupling with N-phenyldiethanolamine and has been characterized by elemental analysis, mass spectrometry, and infrared, UV-vis, and NMR spectroscopies. The chromophoric multilayers have been characterized by X-ray photoelectron and transmission optical spectroscopies, spectroscopic ellipsometry, X-ray reflectivity, advancing contact angle measurements, and polarized second harmonic generation (SHG). The excellent structural regularity of the chromophoric multilayers is indicated by the linear dependence of the [(aminophenyl)azo]pyridinium chromophore longitudinal HOMO → LUMO charge-transfer excitation absorbance at 572 nm and the ellipsometry- and X-ray reflectivity-derived multilayer thicknesses on the number of assembled trilayers, while the uniform polar order of the stacked chromophoric multilayers is evidenced by the quadratic dependence of the second hormonic generation intensities on the number of trilayers. The [(aminophenyl)azo]pyridinium multilayers are photochemically stable, have very high structural regularities, and exhibit a second-order nonlinear optical susceptibility (χ2((2))) of ~3.6 x 10-7 esu (~ 150 pm/V) at a fundamental wavelength of 1064 nm. Finally, atomic force microscopy reveals that the surfaces of the self-assembled multilayers are very smooth (root mean square roughness = 12 {\AA} for a 10 trilayer sample), undoubtedly reflecting the high three-dimensional structural regularities of the individual layers.",
author = "Wenbin Lin and Weiping Lin and Wong, {George K.} and Marks, {Tobin J}",
year = "1996",
month = "8",
day = "28",
doi = "10.1021/ja960395f",
language = "English",
volume = "118",
pages = "8034--8042",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "34",

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TY - JOUR

T1 - Supramolecular approaches to second-order nonlinear optical materials. Self-assembly and microstructural characterization of intrinsically acentric [(aminophenyl)azo]pyridinium superlattices

AU - Lin, Wenbin

AU - Lin, Weiping

AU - Wong, George K.

AU - Marks, Tobin J

PY - 1996/8/28

Y1 - 1996/8/28

N2 - This paper describes the synthesis and characterization of self-assembled second-order nonlinear optical multilayer materials containing the high-hyperpolarizability [(aminophenyl)azo]pyridinium chromophore. The chromophoric multilayers are assembled on clean glass or single-crystal silicon substrates via the following iterative reaction sequence: (1) treatment with 4-ClCH2C6H4SiCl3, 3-BrC3H6SiCl3, or 3-IC3H6SiCl3 to afford a self-assembled coupling layer; (2) quaternization of 4-[[4-[N,N-bis(hydroxylethyl)amino]phenyl]azo]pyridine in a 'topotactic' fashion to generate an [(aminophenyl)azo]pyridinium chromophore layer; (3) cross-linking with octachlorotrisiloxane to afford a capping layer (which also regenerates surface hydroxyl groups for subsequent layer deposition). The new chromophore precursor 4-[[4-[N,N-bis(hydroxylethyl)-amino]phenyl]azo]pyridine was synthesized by diazotization of 4-aminopyridine followed by coupling with N-phenyldiethanolamine and has been characterized by elemental analysis, mass spectrometry, and infrared, UV-vis, and NMR spectroscopies. The chromophoric multilayers have been characterized by X-ray photoelectron and transmission optical spectroscopies, spectroscopic ellipsometry, X-ray reflectivity, advancing contact angle measurements, and polarized second harmonic generation (SHG). The excellent structural regularity of the chromophoric multilayers is indicated by the linear dependence of the [(aminophenyl)azo]pyridinium chromophore longitudinal HOMO → LUMO charge-transfer excitation absorbance at 572 nm and the ellipsometry- and X-ray reflectivity-derived multilayer thicknesses on the number of assembled trilayers, while the uniform polar order of the stacked chromophoric multilayers is evidenced by the quadratic dependence of the second hormonic generation intensities on the number of trilayers. The [(aminophenyl)azo]pyridinium multilayers are photochemically stable, have very high structural regularities, and exhibit a second-order nonlinear optical susceptibility (χ2((2))) of ~3.6 x 10-7 esu (~ 150 pm/V) at a fundamental wavelength of 1064 nm. Finally, atomic force microscopy reveals that the surfaces of the self-assembled multilayers are very smooth (root mean square roughness = 12 Å for a 10 trilayer sample), undoubtedly reflecting the high three-dimensional structural regularities of the individual layers.

AB - This paper describes the synthesis and characterization of self-assembled second-order nonlinear optical multilayer materials containing the high-hyperpolarizability [(aminophenyl)azo]pyridinium chromophore. The chromophoric multilayers are assembled on clean glass or single-crystal silicon substrates via the following iterative reaction sequence: (1) treatment with 4-ClCH2C6H4SiCl3, 3-BrC3H6SiCl3, or 3-IC3H6SiCl3 to afford a self-assembled coupling layer; (2) quaternization of 4-[[4-[N,N-bis(hydroxylethyl)amino]phenyl]azo]pyridine in a 'topotactic' fashion to generate an [(aminophenyl)azo]pyridinium chromophore layer; (3) cross-linking with octachlorotrisiloxane to afford a capping layer (which also regenerates surface hydroxyl groups for subsequent layer deposition). The new chromophore precursor 4-[[4-[N,N-bis(hydroxylethyl)-amino]phenyl]azo]pyridine was synthesized by diazotization of 4-aminopyridine followed by coupling with N-phenyldiethanolamine and has been characterized by elemental analysis, mass spectrometry, and infrared, UV-vis, and NMR spectroscopies. The chromophoric multilayers have been characterized by X-ray photoelectron and transmission optical spectroscopies, spectroscopic ellipsometry, X-ray reflectivity, advancing contact angle measurements, and polarized second harmonic generation (SHG). The excellent structural regularity of the chromophoric multilayers is indicated by the linear dependence of the [(aminophenyl)azo]pyridinium chromophore longitudinal HOMO → LUMO charge-transfer excitation absorbance at 572 nm and the ellipsometry- and X-ray reflectivity-derived multilayer thicknesses on the number of assembled trilayers, while the uniform polar order of the stacked chromophoric multilayers is evidenced by the quadratic dependence of the second hormonic generation intensities on the number of trilayers. The [(aminophenyl)azo]pyridinium multilayers are photochemically stable, have very high structural regularities, and exhibit a second-order nonlinear optical susceptibility (χ2((2))) of ~3.6 x 10-7 esu (~ 150 pm/V) at a fundamental wavelength of 1064 nm. Finally, atomic force microscopy reveals that the surfaces of the self-assembled multilayers are very smooth (root mean square roughness = 12 Å for a 10 trilayer sample), undoubtedly reflecting the high three-dimensional structural regularities of the individual layers.

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