Twisted π-electron system electrooptic chromophores. Structural and electronic consequences of relaxing twist-inducing nonbonded repulsions

Yiliang Wang, David L. Frattarelli, Antonio Facchetti, Elena Cariati, Elisa Tordin, Renato Ugo, Cristiano Zuccaccia, Alceo Macchioni, Staci L. Wegener, Charlotte L. Stern, Mark A Ratner, Tobin J Marks

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Abstract

The synthesis, structural and spectroscopic characterization, and nonlinear optical response properties of a "slightly" twisted zwitterionic 4-quinopyran electrooptic chromophore FMC, 2-{4-[1-(2-propylheptyl)-1H-pyridine- 4-ylidene]cyclohexa-2,5-dienylidene}malononitrile, are reported. X-ray diffraction data and density functional theory (DFT) minimized geometries confirm that deletion of the four o-, o′-, o″-, and o‴-methyl groups in the parent chromophore TMC-2, 2-{4-[3,5-dimethyl-1-(2-propylheptyl)- 1H-pyridin-4-ylidene]-3,5-dimethylcyclohexa-2,5-dienylidene}malononitrile, relaxes the arene-arene twist angle from 89.6 to 9.0°. These geometrical changes result in a significantly increased contribution of the quinoidal structure to the molecular ground state of FMC (versus TMC-2), reduced solvatochromic shifts in the optical spectra, and a diminished electric-field-induced second-harmonic (EFISH) generation derived molecular hyperpolarizability (μβ = -2340 × 10-48 esu of DFMC, the dendrimer derivative of FMC, vs -24000 × 10-48 esu of TMC-2) in CH2Cl2 at 1907 nm. Pulsed field gradient spin-echo (PGSE) NMR spectroscopy and EFISH indicate that the levels of FMC aggregation in solution are comparable to those of TMC-2 (monomers and dimers) in CH2Cl2 solution. B3LYP and INDO/S computation of chromophore molecular structure, aggregation, and hyperpolarizability trends are in good agreement with experiment.

Original languageEnglish
Pages (from-to)8005-8015
Number of pages11
JournalJournal of Physical Chemistry C
Volume112
Issue number21
DOIs
Publication statusPublished - May 29 2008

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Chromophores
Electrooptical effects
chromophores
electro-optics
malononitrile
Electrons
Agglomeration
Electric fields
electronics
Dendrimers
deletion
electrons
electric fields
dendrimers
Harmonic generation
Dimers
Pyridine
Ground state
Molecular structure
Nuclear magnetic resonance spectroscopy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Twisted π-electron system electrooptic chromophores. Structural and electronic consequences of relaxing twist-inducing nonbonded repulsions. / Wang, Yiliang; Frattarelli, David L.; Facchetti, Antonio; Cariati, Elena; Tordin, Elisa; Ugo, Renato; Zuccaccia, Cristiano; Macchioni, Alceo; Wegener, Staci L.; Stern, Charlotte L.; Ratner, Mark A; Marks, Tobin J.

In: Journal of Physical Chemistry C, Vol. 112, No. 21, 29.05.2008, p. 8005-8015.

Research output: Contribution to journalArticle

Wang, Y, Frattarelli, DL, Facchetti, A, Cariati, E, Tordin, E, Ugo, R, Zuccaccia, C, Macchioni, A, Wegener, SL, Stern, CL, Ratner, MA & Marks, TJ 2008, 'Twisted π-electron system electrooptic chromophores. Structural and electronic consequences of relaxing twist-inducing nonbonded repulsions', Journal of Physical Chemistry C, vol. 112, no. 21, pp. 8005-8015. https://doi.org/10.1021/jp8003135
Wang, Yiliang ; Frattarelli, David L. ; Facchetti, Antonio ; Cariati, Elena ; Tordin, Elisa ; Ugo, Renato ; Zuccaccia, Cristiano ; Macchioni, Alceo ; Wegener, Staci L. ; Stern, Charlotte L. ; Ratner, Mark A ; Marks, Tobin J. / Twisted π-electron system electrooptic chromophores. Structural and electronic consequences of relaxing twist-inducing nonbonded repulsions. In: Journal of Physical Chemistry C. 2008 ; Vol. 112, No. 21. pp. 8005-8015.
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