Design, Synthesis, and Structural and Spectroscopic Studies of Push-Pull Two-Photon Absorbing Chromophores with Acceptor Groups of Varying Strength

    Authors

    A. R. Morales; A. Frazer; A. W. Woodward; H. Y. Ahn-White; A. Fonari; P. Tongwa; T. Timofeeva;K. D. Belfield

    Comments

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    Abbreviated Journal Title

    J. Org. Chem.

    Keywords

    NONLINEAR-OPTICAL CHROMOPHORES; FLUORENYL-BASED CHROMOPHORES; ORGANIC; MATERIALS; CROSS-SECTIONS; ABSORPTION; DERIVATIVES; DENSITY; EXCITATION; MOLECULES; DIPOLAR; Chemistry, Organic

    Abstract

    A new series of unsymmetrical diphenylaminofluorene-based chromophores with various strong g-electron acceptors were synthesized and fully characterized. The systematic alteration of the structural design facilitated the investigation of effects such as molecular symmetry and strength of electron-donating and/or -withdrawing termini have on optical nonlinearity. In order to determine the electronic and geometrical properties of the novel compounds, a thorough investigation was carried out by a combination of linear and nonlinear spectroscopic techniques, single-crystal X-ray diffraction, and quantum chemical calculations. Finally, on the basis of two-photon absorption (2PA) cross sections, the general trend for pi-electron accepting ability, i.e., ability to accept charge transfer from diphenylamine was: 2-pyran-4-ylidene malononitrile (pyranone) > dicyanovinyl > bis(dicyanomethylidene)indane > 1-(thiophen-2-yl)propenone > dicyanoethylenyl > 3-(thiophen-2-yl)propenone. An analogue with the 2-pyran-4-ylidene malononitrile acceptor group exhibited a nearly 3-fold enhancement of the 2PA cross section (1650 GM at 840 nm), relative to other members of the series.

    Journal Title

    Journal of Organic Chemistry

    Volume

    78

    Issue/Number

    3

    Publication Date

    1-1-2013

    Document Type

    Article

    Language

    English

    First Page

    1014

    Last Page

    1025

    WOS Identifier

    WOS:000314558300020

    ISSN

    0022-3263

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