Building blocks for N-type molecular and polymeric electronics. Perfluoroalkyl- versus alkyl-functionalized oligothiophenes (nTs; n = 2-6). Systematic synthesis, spectroscopy, electrochemistry, and solid-state organization

Antonio Facchetti, Myung Han Yoon, Charlotte L. Stern, Geoffrey R. Hutchison, Mark A Ratner, Tobin J Marks

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Abstract

The synthesis, comparative physicochemical properties, and solid-state structures of five oligothiophene (nT) series differing in substituent nature and attachment, regiochemistry, and oligothiophene core length (n) are described. These five series include the following 25 compounds: (i) α,ω-diperfluorohexyl-nTs 1 (DFH-nTs, n = 2-6), (ii) β,β′-diperfluorohexyl-nTs 2 (isoDFH-nTs, n = 2-6), (iii) α,ω-dihexyl-nTs 3 (DH-nTs, n = 2-6), (iv) β,β′- dihexyl-nTs 4 (isoDH-nTs, n = 2-6), and (v) unsubstituted oligothiophenes 5 (αnTs, n = 2-6). All new compounds were characterized by elemental analysis, mass spectrometry, and multinuclear NMR spectroscopy. To probe and address quantitatively how the chemistry and regiochemistry of conjugated core substitution affects molecular and solid-state properties, the entire 1-5 series was investigated by differential scanning calorimetry, thermogravimetric analysis, and optical absorption and emission spectroscopies. Single-crystal X-ray diffraction data for several fluorocarbon-substituted oligomers are also presented and compared. The combined analysis of these data indicates that fluorocarbon-substituted nT molecules strongly interact in the condensed state, with unit cell level phase separation between the aromatic core and fluorocarbon chains. Surprisingly, despite these strong intermolecular interactions, high solid-state fluorescence efficiencies are exhibited by the fluorinated derivatives. Insight into the solution molecular geometries and conformational behavior are obtained from analysis of optical and variable-temperature NMR spectra. Finally, cyclic voltammetry data offer a reliable picture of frontier MO energies, which, in combination with DFT computations, provide key information on relationships between oligothiophene substituent effects and electronic response properties.

Original languageEnglish
Pages (from-to)13480-13501
Number of pages22
JournalJournal of the American Chemical Society
Volume126
Issue number41
DOIs
Publication statusPublished - Oct 20 2004

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Electrochemistry
Fluorocarbons
Spectrum Analysis
Electronic equipment
Spectroscopy
Biomolecular Nuclear Magnetic Resonance
Differential Scanning Calorimetry
Emission spectroscopy
Absorption spectroscopy
Oligomers
Discrete Fourier transforms
X-Ray Diffraction
Phase separation
Light absorption
Nuclear magnetic resonance spectroscopy
Cyclic voltammetry
Mass spectrometry
Thermogravimetric analysis
Differential scanning calorimetry
Mass Spectrometry

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{cebe3a3ffb7b43c5999ecfc95e1672eb,
title = "Building blocks for N-type molecular and polymeric electronics. Perfluoroalkyl- versus alkyl-functionalized oligothiophenes (nTs; n = 2-6). Systematic synthesis, spectroscopy, electrochemistry, and solid-state organization",
abstract = "The synthesis, comparative physicochemical properties, and solid-state structures of five oligothiophene (nT) series differing in substituent nature and attachment, regiochemistry, and oligothiophene core length (n) are described. These five series include the following 25 compounds: (i) α,ω-diperfluorohexyl-nTs 1 (DFH-nTs, n = 2-6), (ii) β,β′-diperfluorohexyl-nTs 2 (isoDFH-nTs, n = 2-6), (iii) α,ω-dihexyl-nTs 3 (DH-nTs, n = 2-6), (iv) β,β′- dihexyl-nTs 4 (isoDH-nTs, n = 2-6), and (v) unsubstituted oligothiophenes 5 (αnTs, n = 2-6). All new compounds were characterized by elemental analysis, mass spectrometry, and multinuclear NMR spectroscopy. To probe and address quantitatively how the chemistry and regiochemistry of conjugated core substitution affects molecular and solid-state properties, the entire 1-5 series was investigated by differential scanning calorimetry, thermogravimetric analysis, and optical absorption and emission spectroscopies. Single-crystal X-ray diffraction data for several fluorocarbon-substituted oligomers are also presented and compared. The combined analysis of these data indicates that fluorocarbon-substituted nT molecules strongly interact in the condensed state, with unit cell level phase separation between the aromatic core and fluorocarbon chains. Surprisingly, despite these strong intermolecular interactions, high solid-state fluorescence efficiencies are exhibited by the fluorinated derivatives. Insight into the solution molecular geometries and conformational behavior are obtained from analysis of optical and variable-temperature NMR spectra. Finally, cyclic voltammetry data offer a reliable picture of frontier MO energies, which, in combination with DFT computations, provide key information on relationships between oligothiophene substituent effects and electronic response properties.",
author = "Antonio Facchetti and Yoon, {Myung Han} and Stern, {Charlotte L.} and Hutchison, {Geoffrey R.} and Ratner, {Mark A} and Marks, {Tobin J}",
year = "2004",
month = "10",
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doi = "10.1021/ja048988a",
language = "English",
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T1 - Building blocks for N-type molecular and polymeric electronics. Perfluoroalkyl- versus alkyl-functionalized oligothiophenes (nTs; n = 2-6). Systematic synthesis, spectroscopy, electrochemistry, and solid-state organization

AU - Facchetti, Antonio

AU - Yoon, Myung Han

AU - Stern, Charlotte L.

AU - Hutchison, Geoffrey R.

AU - Ratner, Mark A

AU - Marks, Tobin J

PY - 2004/10/20

Y1 - 2004/10/20

N2 - The synthesis, comparative physicochemical properties, and solid-state structures of five oligothiophene (nT) series differing in substituent nature and attachment, regiochemistry, and oligothiophene core length (n) are described. These five series include the following 25 compounds: (i) α,ω-diperfluorohexyl-nTs 1 (DFH-nTs, n = 2-6), (ii) β,β′-diperfluorohexyl-nTs 2 (isoDFH-nTs, n = 2-6), (iii) α,ω-dihexyl-nTs 3 (DH-nTs, n = 2-6), (iv) β,β′- dihexyl-nTs 4 (isoDH-nTs, n = 2-6), and (v) unsubstituted oligothiophenes 5 (αnTs, n = 2-6). All new compounds were characterized by elemental analysis, mass spectrometry, and multinuclear NMR spectroscopy. To probe and address quantitatively how the chemistry and regiochemistry of conjugated core substitution affects molecular and solid-state properties, the entire 1-5 series was investigated by differential scanning calorimetry, thermogravimetric analysis, and optical absorption and emission spectroscopies. Single-crystal X-ray diffraction data for several fluorocarbon-substituted oligomers are also presented and compared. The combined analysis of these data indicates that fluorocarbon-substituted nT molecules strongly interact in the condensed state, with unit cell level phase separation between the aromatic core and fluorocarbon chains. Surprisingly, despite these strong intermolecular interactions, high solid-state fluorescence efficiencies are exhibited by the fluorinated derivatives. Insight into the solution molecular geometries and conformational behavior are obtained from analysis of optical and variable-temperature NMR spectra. Finally, cyclic voltammetry data offer a reliable picture of frontier MO energies, which, in combination with DFT computations, provide key information on relationships between oligothiophene substituent effects and electronic response properties.

AB - The synthesis, comparative physicochemical properties, and solid-state structures of five oligothiophene (nT) series differing in substituent nature and attachment, regiochemistry, and oligothiophene core length (n) are described. These five series include the following 25 compounds: (i) α,ω-diperfluorohexyl-nTs 1 (DFH-nTs, n = 2-6), (ii) β,β′-diperfluorohexyl-nTs 2 (isoDFH-nTs, n = 2-6), (iii) α,ω-dihexyl-nTs 3 (DH-nTs, n = 2-6), (iv) β,β′- dihexyl-nTs 4 (isoDH-nTs, n = 2-6), and (v) unsubstituted oligothiophenes 5 (αnTs, n = 2-6). All new compounds were characterized by elemental analysis, mass spectrometry, and multinuclear NMR spectroscopy. To probe and address quantitatively how the chemistry and regiochemistry of conjugated core substitution affects molecular and solid-state properties, the entire 1-5 series was investigated by differential scanning calorimetry, thermogravimetric analysis, and optical absorption and emission spectroscopies. Single-crystal X-ray diffraction data for several fluorocarbon-substituted oligomers are also presented and compared. The combined analysis of these data indicates that fluorocarbon-substituted nT molecules strongly interact in the condensed state, with unit cell level phase separation between the aromatic core and fluorocarbon chains. Surprisingly, despite these strong intermolecular interactions, high solid-state fluorescence efficiencies are exhibited by the fluorinated derivatives. Insight into the solution molecular geometries and conformational behavior are obtained from analysis of optical and variable-temperature NMR spectra. Finally, cyclic voltammetry data offer a reliable picture of frontier MO energies, which, in combination with DFT computations, provide key information on relationships between oligothiophene substituent effects and electronic response properties.

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