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Push–Pull Macrocycles: Donor–Acceptor Compounds with Paired Linearly Conjugated or Cross-Conjugated Pathways

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    Push–Pull Macrocycles: Donor–Acceptor Compounds with Paired Linearly Conjugated or Cross-Conjugated Pathways
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    Department of Chemistry & Biochemistry, Miami University, Oxford, Ohio 45056, United States
    *E-mail: [email protected]
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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2012, 77, 5, 2285–2298
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    https://doi.org/10.1021/jo2026004
    Published February 2, 2012
    Copyright © 2012 American Chemical Society
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    Abstract

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    Two-dimensional π-systems are of current interest in the design of functional organic molecules, exhibiting unique behavior for applications in organic electronics, single-molecule devices, and sensing. Here we describe the synthesis and characterization of “push–pull macrocycles”: electron-rich and electron-poor moieties linked by a pair of (matched) conjugated bridges. We have developed a two-component macrocyclization strategy that allows these structures to be synthesized with efficiencies comparable to acyclic donor–bridge–acceptor systems. Compounds with both cross-conjugated (m-phenylene) and linearly conjugated (2,5-thiophene) bridges have been prepared. As expected, the compounds undergo excitation to locally excited states followed by fluorescence from charge-transfer states. The m-phenylene-based systems exhibit slower charge-recombination rates presumably due to reduced electronic coupling through the cross-conjugated bridges. Interestingly, pairing the linearly conjugated 2,5-thiophene bridges also slows charge recombination. DFT calculations of frontier molecular orbitals show that the direct HOMO–LUMO transition is polarized orthogonal to the axis of charge transfer for these symmetrical macrocyclic architectures, reducing the electronic coupling. We believe the push–pull macrocycle design may be useful in engineering functional frontier molecular orbital symmetries.

    Copyright © 2012 American Chemical Society

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    Supporting Information

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    Solvatochromism of UV–vis spectra; fluorescence spectra for symmetrical compounds; Lippert–Mataga plots in cyclohexane/CH2Cl2 mixtures; TCSPC measurements; optimized geometries of symmetrical compounds; TD-DFT calculated UV–vis spectra; energies, zero-point vibrational energy corrections, and Cartesian coordinates of optimized geometries; complete ref 95; NMR spectra of all isolated compounds. This material is available free of charge via the Internet at http://pubs.acs.org.

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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2012, 77, 5, 2285–2298
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jo2026004
    Published February 2, 2012
    Copyright © 2012 American Chemical Society
    Request reuse permissions

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