ja0674690_si_008.cif (24.98 kB)
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
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posted on 2007-03-21, 00:00 authored by 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. MarksThis 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 μβ 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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NMR spectroscopic studiescentrosymmetric aggregatesNonlinear Optical Propertieschromophoreaggregationnonresonant μβtwist angleNOE NMR measurementsEOfield gradientComputational StudiesThis contribution details1907 nmfluorescence spectroscopyPGSE1310 nmEFISHground stateDCCrystallographic analysisNMR spectroscopyIRsolution phasehyperpolarizabilitiesolvation effectsElectronic Structures
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