A series of fully methylthiolated bi-, ter-, and quatertetrathiafulvalenes have been synthesized using cross- and homocoupling reactions of tetrathiafulvalenylzinc derivatives; the tetracation-tetraradical derived from the helical tetrathiafulvalene tetramer exhibits an intramolecular association of the terminal cation-radicals.
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http://dx.doi.org/10.1021/ol0000915 | DOI Listing |
Nanomaterials (Basel)
November 2020
Institute of Solid State Physics, NAWI Graz, Graz University of Technology, Petersgasse 16, 8010 Graz, Austria.
In recent years, charge transport in metal-organic frameworks (MOFs) has shifted into the focus of scientific research. In this context, systems with efficient through-space charge transport pathways resulting from -stacked conjugated linkers are of particular interest. In the current manuscript, we use density functional theory-based simulations to provide a detailed understanding of such MOFs, which, in the present case, are derived from the prototypical Zn(TTFTB) system (with TTFTB corresponding to tetrathiafulvalene tetrabenzoate).
View Article and Find Full Text PDFACS Appl Mater Interfaces
March 2020
Department of Chemistry, Clemson University, Clemson, South Carolina 29634, United States.
To diversify metal-organic framework (MOF) structures beyond traditional Euclidean geometries and to create new charge-delocalization pathways beneficial for electrical conductivity, we constructed a novel double-helical MOF (dhMOF) by introducing a new butterfly-shaped electron-rich π-extended tetrathiafulvalene ligand equipped with four benzoate groups (ExTTFTB). The face-to-face oriented convex ExTTFTB ligands connected by Zn(COO) paddlewheel nodes formed ovoid cavities suitable for guest encapsulation, while π-π-interaction between the ExTTFTB ligands of neighboring strands helped create new charge-delocalization pathways in iodine-mediated partially oxidized dhMOF. Iodine vapor diffusion led to oxidation of half of the ExTTFTB ligands in each double-helical strand to ExTTFTB radical cations, which putatively formed intermolecular ExTTFTB/ExTTFTB π-donor/acceptor charge-transfer chains with the neutral ExTTFTB ligands of an adjacent strand, creating supramolecular wire-like charge-delocalization pathways along the helix seams.
View Article and Find Full Text PDFInorg Chem
December 2019
Division of Chemistry, Graduate School of Science , Kyoto University, Kitashirakawa-Oiwakecho , Sakyo-ku, Kyoto 606-8502 , Japan.
Rational control of the molecular arrangement in solids has been the subject of intense research for many years. In particular, the structural control of bis(ethylenedithio)tetrathiafulvalene (ET) radical cations has attracted special interest because of the primary effect on the electronic properties of the salts. In this study, we obtained the first ET cation radical salts formed with nonuniform silver(I) complex polyanions, which involve multiple kinds of openings in the anionic layer, by an electrocrystallization method.
View Article and Find Full Text PDFActa Crystallogr E Crystallogr Commun
August 2019
Department of Chemistry, New Mexico Highlands University, Las Vegas, New Mexico, 87701, USA.
The mol-ecule of the title compound, CHBrS, has a C-shape, with mol-ecular symmetry. The dihedral angle between the planes of the di-thiol and phenyl rings is 8.35 (9)°.
View Article and Find Full Text PDFChem Commun (Camb)
May 2019
Laboratoire MOLTECH-Anjou, UMR CNRS 6200, UNIV Angers, SFR MATRIX, 2 Bd Lavoisier, 49045 Angers Cedex, France.
Tetrathiafulvalene redox units were grafted at both extremities of an oligopyridine-dicarboxamide foldamer through a straightforward copper-catalyzed azide-alkyne cycloaddition. The present work demonstrates that the hybridization equilibrium of foldamers can be tuned through redox stimulations.
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