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Synthesis and Properties of Conjugated Oligoyne-Centered π-Extended Tetrathiafulvalene Analogues and Related Macromolecular Systems

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    Synthesis and Properties of Conjugated Oligoyne-Centered π-Extended Tetrathiafulvalene Analogues and Related Macromolecular Systems
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    † Department of Chemistry, Memorial University of Newfoundland, St. John’s, Newfoundland A1B 3X7, Canada
    ‡ Rigaku Americas Corporation, 9009 New Trails Drive, The Woodlands, Texas 77381, United States
    *E-mail: [email protected]
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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2011, 76, 8, 2701–2715
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    https://doi.org/10.1021/jo2000447
    Published March 8, 2011
    Copyright © 2011 American Chemical Society
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    Abstract

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    Alkynyl-substituted phenyldithiafulvenes have been found to act as versatile building blocks for the construction of π-conjugated molecular rods, shape-persistent macrocycles (SPMs), and conducting polymers. Through Cu(I)-catalyzed alkynyl homocoupling, a series of linear-shaped π-extended tetrathiafulvalene analogues (exTTFs) carrying conjugated oligoynes (ranging from diyne to hexayne) as the central π-bridge were readily prepared. The solid-state properties and reactivities of diyne- and tetrayne-centered exTTFs were characterized by X-ray crystallography and differential scanning calorimetry (DSC), while the electronic properties of the oligoyne-exTTFs were elucidated by UV−vis absorption spectroscopy and density functional theory (DFT) calculations. Cyclic voltammetric analysis showed that the terminal phenyldithiafulvene groups of the oligyne-exTTFs could undergo oxidative coupling to form tetrathiafulvalene vinylogue (TTFV)-linked polymer wires. Through a different synthetic route involving oxidative dimerization and Pd/Cu-catalyzed alkynyl homocoupling, the acetylenic phenyldithiafulvene precursors led to shape-persistent macrocycles where the formation of trimeric macrocycles was particularly favored due to the small ring strain incurred. Finally, spectroelectrochemical studies on these oligoyne and TTF hybrid materials disclosed electrochromic and molecular redox-controlled switching properties applicable to molecular electronic and optoelectronic devices.

    Copyright © 2011 American Chemical Society

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    1H and 13C NMR spectroscopic characterizations for all new compounds, mass spectrometric data for 18, P1, and P2, computational details for oligoyne-exTTFs 16−18 and macrocycle 21, and X-ray crystallographic data for 16 and 17. 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. 2011, 76, 8, 2701–2715
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jo2000447
    Published March 8, 2011
    Copyright © 2011 American Chemical Society
    Request reuse permissions

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