Probing the symmetry of the nonlinear optic chromophore Ru(trans-4,4'- diethylaminostyryl-2,2'-bipyridine)32+: Insight from polarized hyper- Rayleigh scattering and electroabsorption (Stark) spectroscopy

Fredrick W. Vance, Joseph T Hupp

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Abstract

Polarized hyper-Rayleigh scattering (HRS) has been used to interrogate a putative octupolar 'super' chromophore Ru(trans-4,4'-diethylaminostyryl- 2,2'-bipyridine)32+. While the hyperpolarizability (β) is impressive, it is apparent from polarized HRS measurements that the symmetry of the excited state, and thus the hyperpolarizability tensor, is best described as dipolar in nature. Electroabsorption (electronic Stark effect) experiments support these findings, implying that changes in dipole moment (Δμ) accompany optical excitation. The measured |Δμ| contributions from both metal-to- ligand charge transfer and intraligand transitions have been used to model the wavelength-dependent hyperpolarizability; reasonable qualitative agreement between experimental results and a simple three-state, two-level dipolar model is obtained.

Original languageEnglish
Pages (from-to)4047-4053
Number of pages7
JournalJournal of the American Chemical Society
Volume121
Issue number16
DOIs
Publication statusPublished - Apr 28 1999

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2,2'-Dipyridyl
Nonlinear optics
Rayleigh scattering
Chromophores
Spectrum Analysis
Metals
Spectroscopy
Ligands
Stark effect
Photoexcitation
Dipole moment
Crystal symmetry
Excited states
Tensors
Charge transfer
Wavelength
Experiments
dichlorotetrakis(dimethyl sulfoxide)ruthenium II

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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abstract = "Polarized hyper-Rayleigh scattering (HRS) has been used to interrogate a putative octupolar 'super' chromophore Ru(trans-4,4'-diethylaminostyryl- 2,2'-bipyridine)32+. While the hyperpolarizability (β) is impressive, it is apparent from polarized HRS measurements that the symmetry of the excited state, and thus the hyperpolarizability tensor, is best described as dipolar in nature. Electroabsorption (electronic Stark effect) experiments support these findings, implying that changes in dipole moment (Δμ) accompany optical excitation. The measured |Δμ| contributions from both metal-to- ligand charge transfer and intraligand transitions have been used to model the wavelength-dependent hyperpolarizability; reasonable qualitative agreement between experimental results and a simple three-state, two-level dipolar model is obtained.",
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T1 - Probing the symmetry of the nonlinear optic chromophore Ru(trans-4,4'- diethylaminostyryl-2,2'-bipyridine)32+

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