The synthesis of phosphines with light controlled basicity is presented in this study. A methodological approach for the preparation of these unconventional photochromic phosphines based on a dithienylethene organic moiety is reported. It relies on the palladium-catalyzed annulation of alkynyl phosphines in the presence of a 2,3-Dithienylsilacyclopropene. Accordingly, a diphenyphosphino moiety is connected to the organic photochrome thanks to different linkers. Their influence on the photochromism and on the phosphinyl group basicity is studied and evaluated based on experimental an NMR descriptor as well as DFT calculations.
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http://dx.doi.org/10.1002/chem.202302374 | DOI Listing |
Chem Commun (Camb)
October 2023
Westfälische Wilhelms-Universität Münster, Institut für Anorganische und Analytische Chemie, Corrensstraße 30, Münster 48149, Germany.
The synthesis and properties of photoswitchable electron-rich phosphines containing N-heterocyclic imines equipped with a photochromic dithienylethene unit are reported. Heteronuclear NMR spectroscopy and UV/vis studies reveal that the imine substituents undergo reversible electrocyclic ring-closing and ring-opening reactions upon exposure to UV and visible light, respectively. The photoisomerization alters the electron-donating ability of the phosphines by up to ΔTEP = 8 cm.
View Article and Find Full Text PDFChemistry
November 2023
ISCR (Institut des Sciences Chimiques de Rennes), UMR 6226, Univ Rennes, CNRS, 35000, Rennes, France.
The synthesis of phosphines with light controlled basicity is presented in this study. A methodological approach for the preparation of these unconventional photochromic phosphines based on a dithienylethene organic moiety is reported. It relies on the palladium-catalyzed annulation of alkynyl phosphines in the presence of a 2,3-Dithienylsilacyclopropene.
View Article and Find Full Text PDFChemphyschem
December 2019
Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
Anion binding to a receptor based on stiff-stilbene, which is equipped with a urea hydrogen bond donating group and a phosphate or phosphinate hydrogen bond accepting group, can be controlled by light. In one photoaddressable state (E isomer) the urea binding site is available for binding, while in the other (Z isomer) it is blocked because of an intramolecular interaction with its hydrogen bond accepting motif. This intramolecular interaction is supported by DFT calculations and H NMR titrations reveal a significantly lower anion binding strength for the state in which anion binding is blocked.
View Article and Find Full Text PDFChemistry
July 2018
Department of Chemistry, University of British Columbia, Vancouver, British Columbia, Canada.
Metal-containing dithienylethenes offer new opportunities for variations in photochromic behavior. This work reports a series of copper(I) complexes containing dithienylethene-based bidentate phosphine ligands displaying varying photochromic properties. A copper dimer is used as a common precursor, allowing diverse photochromic functionality to be achieved.
View Article and Find Full Text PDFJ Pept Sci
July 2017
Institut für Chemie, Technische Universität Berlin, Str. des 17. Juni 135, 10623, Berlin, Germany.
The 4,5,6-trimethoxy-2-mercaptobenzyl auxiliary was used in auxiliary-based native chemical ligation reactions with Boc-protected pHTI and mHTI ω-amino acid thioesters 2a,b for the construction of small hemithioindigo (HTI)-based chromopeptides 6a,b with a class 1 PDZ binding motif. While reversible tris(2-carboxyethyl)phosphine (TCEP)-HTI adduct formation required moderate use of access TCEP, the Na ascorbate concentration was broadly varied for optimization of the reaction conditions. In the studies presented, the mHTI ω-amino acid thioester 2b proved to be slightly less reactive than the pHTI ω-amino acid thioester 2a.
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