Ultralarge hyperpolarizability twisted π-electron system electro-optic chromophores: Synthesis, solid-state and solution-phase structural characteristics, electronic structures, linear and nonlinear optical properties, and computational studies

Hu Kang, Antonio Facchetti, Hua Jiang, Elena Cariati, Stefania Righetto, Renato Ugo, Cristiano Zuccaccia, Alceo Macchioni, Charlotte L. Stern, Zhifu Liu, Seng Tiong Ho, Eric C. Brown, Mark A Ratner, Tobin J Marks

Research output: Contribution to journalArticle

210 Citations (Scopus)

Abstract

This contribution details the synthesis and chemical/physical characterization of a series of unconventional twisted π-electron system electro-optic (EO) chromophores. Crystallographic analysis of these chromophores reveals large ring-ring dihedral twist angles (80-89°) and a highly charge-separated zwitterionic structure dominating the ground state. NOE NMR measurements of the twist angle in solution confirm that the solid-state twisting persists essentially unchanged in solution. Optical, IR, and NMR spectroscopic studies in both the solution phase and solid state further substantiate that the solid-state structural characteristics persist in solution. The aggregation of these highly polar zwitterions is investigated using several experimental techniques, including concentration-dependent optical and fluorescence spectroscopy and pulsed field gradient spin-echo (PGSE) NMR spectroscopy in combination with solid-state data. These studies reveal clear evidence of the formation of centrosymmetric aggregates in concentrated solutions and in the solid state and provide quantitative information on the extent of aggregation. Solution-phase DC electric-field-induced second-harmonic generation (EFISH) measurements reveal unprecedented hyperpolarizabilities (nonresonant πβ as high as -488 000 × 10-48 esu at 1907 nm). Incorporation of these chromophores into guest-host poled polyvinylphenol films provides very large electro-optic coefficients (r33) of ≃330 pm/V at 1310 nm. The aggregation and structure-property effects on the observed linear/nonlinear optical properties are discussed. High-level computations based on state-averaged complete active space self-consistent field (SA-CASSCF) methods provide a new rationale for these exceptional hyperpolarizabilities and demonstrate significant solvation effects on hyperpolarizabilities, in good agreement with experiment. As such, this work suggests new paradigms for molecular hyperpolarizabilities and electro-optics.

Original languageEnglish
Pages (from-to)3267-3286
Number of pages20
JournalJournal of the American Chemical Society
Volume129
Issue number11
DOIs
Publication statusPublished - Mar 21 2007

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Chromophores
Electrooptical effects
Electronic structure
Optical properties
Electrons
Agglomeration
Nuclear magnetic resonance
Fluorescence Spectrometry
Solvation
Fluorescence spectroscopy
Dihedral angle
Harmonic generation
Ground state
Nuclear magnetic resonance spectroscopy
Magnetic Resonance Spectroscopy
Electric fields
Experiments

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Ultralarge hyperpolarizability twisted π-electron system electro-optic chromophores : Synthesis, solid-state and solution-phase structural characteristics, electronic structures, linear and nonlinear optical properties, and computational studies. / Kang, Hu; Facchetti, Antonio; Jiang, Hua; Cariati, Elena; Righetto, Stefania; Ugo, Renato; Zuccaccia, Cristiano; Macchioni, Alceo; Stern, Charlotte L.; Liu, Zhifu; Ho, Seng Tiong; Brown, Eric C.; Ratner, Mark A; Marks, Tobin J.

In: Journal of the American Chemical Society, Vol. 129, No. 11, 21.03.2007, p. 3267-3286.

Research output: Contribution to journalArticle

Kang, Hu ; Facchetti, Antonio ; Jiang, Hua ; Cariati, Elena ; Righetto, Stefania ; Ugo, Renato ; Zuccaccia, Cristiano ; Macchioni, Alceo ; Stern, Charlotte L. ; Liu, Zhifu ; Ho, Seng Tiong ; Brown, Eric C. ; Ratner, Mark A ; Marks, Tobin J. / Ultralarge hyperpolarizability twisted π-electron system electro-optic chromophores : Synthesis, solid-state and solution-phase structural characteristics, electronic structures, linear and nonlinear optical properties, and computational studies. In: Journal of the American Chemical Society. 2007 ; Vol. 129, No. 11. pp. 3267-3286.
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abstract = "This contribution details the synthesis and chemical/physical characterization of a series of unconventional twisted π-electron system electro-optic (EO) chromophores. Crystallographic analysis of these chromophores reveals large ring-ring dihedral twist angles (80-89°) and a highly charge-separated zwitterionic structure dominating the ground state. NOE NMR measurements of the twist angle in solution confirm that the solid-state twisting persists essentially unchanged in solution. Optical, IR, and NMR spectroscopic studies in both the solution phase and solid state further substantiate that the solid-state structural characteristics persist in solution. The aggregation of these highly polar zwitterions is investigated using several experimental techniques, including concentration-dependent optical and fluorescence spectroscopy and pulsed field gradient spin-echo (PGSE) NMR spectroscopy in combination with solid-state data. These studies reveal clear evidence of the formation of centrosymmetric aggregates in concentrated solutions and in the solid state and provide quantitative information on the extent of aggregation. Solution-phase DC electric-field-induced second-harmonic generation (EFISH) measurements reveal unprecedented hyperpolarizabilities (nonresonant πβ as high as -488 000 × 10-48 esu at 1907 nm). Incorporation of these chromophores into guest-host poled polyvinylphenol films provides very large electro-optic coefficients (r33) of ≃330 pm/V at 1310 nm. The aggregation and structure-property effects on the observed linear/nonlinear optical properties are discussed. High-level computations based on state-averaged complete active space self-consistent field (SA-CASSCF) methods provide a new rationale for these exceptional hyperpolarizabilities and demonstrate significant solvation effects on hyperpolarizabilities, in good agreement with experiment. As such, this work suggests new paradigms for molecular hyperpolarizabilities and electro-optics.",
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T2 - Synthesis, solid-state and solution-phase structural characteristics, electronic structures, linear and nonlinear optical properties, and computational studies

AU - Kang, Hu

AU - Facchetti, Antonio

AU - Jiang, Hua

AU - Cariati, Elena

AU - Righetto, Stefania

AU - Ugo, Renato

AU - Zuccaccia, Cristiano

AU - Macchioni, Alceo

AU - Stern, Charlotte L.

AU - Liu, Zhifu

AU - Ho, Seng Tiong

AU - Brown, Eric C.

AU - Ratner, Mark A

AU - Marks, Tobin J

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N2 - This contribution details the synthesis and chemical/physical characterization of a series of unconventional twisted π-electron system electro-optic (EO) chromophores. Crystallographic analysis of these chromophores reveals large ring-ring dihedral twist angles (80-89°) and a highly charge-separated zwitterionic structure dominating the ground state. NOE NMR measurements of the twist angle in solution confirm that the solid-state twisting persists essentially unchanged in solution. Optical, IR, and NMR spectroscopic studies in both the solution phase and solid state further substantiate that the solid-state structural characteristics persist in solution. The aggregation of these highly polar zwitterions is investigated using several experimental techniques, including concentration-dependent optical and fluorescence spectroscopy and pulsed field gradient spin-echo (PGSE) NMR spectroscopy in combination with solid-state data. These studies reveal clear evidence of the formation of centrosymmetric aggregates in concentrated solutions and in the solid state and provide quantitative information on the extent of aggregation. Solution-phase DC electric-field-induced second-harmonic generation (EFISH) measurements reveal unprecedented hyperpolarizabilities (nonresonant πβ as high as -488 000 × 10-48 esu at 1907 nm). Incorporation of these chromophores into guest-host poled polyvinylphenol films provides very large electro-optic coefficients (r33) of ≃330 pm/V at 1310 nm. The aggregation and structure-property effects on the observed linear/nonlinear optical properties are discussed. High-level computations based on state-averaged complete active space self-consistent field (SA-CASSCF) methods provide a new rationale for these exceptional hyperpolarizabilities and demonstrate significant solvation effects on hyperpolarizabilities, in good agreement with experiment. As such, this work suggests new paradigms for molecular hyperpolarizabilities and electro-optics.

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