The reactions of the ditopic ligand 1,4-bis(2,2':6',2″-terpyridin-4'-yl)benzene (1) as well as the monotopic ligands 4'-phenyl-2,2':6',2″-terpyridine (2) and 2,2':6',2″-terpyridine (3) with Fe(2+), Co(2+), and Ni(2+) in solution are studied. While the reaction of 1 with Fe(2+), Co(2+), and Ni(2+) results in metallo-supramolecular coordination polyelectrolytes (MEPEs), ligands 2 and 3 give mononuclear complexes. All compounds are analyzed by UV/vis and fluorescence spectroscopy. Fluorescence spectroscopy indicates that protonation as well as coordination to Zn(2+) leads to an enhanced fluorescence of the terpyridine ligands. In contrast, Fe(2+), Co(2+), or Ni(2+) quench the fluorescence of the ligands. The kinetics of the reactions are studied by stopped-flow fluorescence spectroscopy. Analysis of the measured data is presented and the full kinetic rate laws for the coordination of the terpyridine ligands 1, 2, and 3 to Fe(2+), Co(2+), and Ni(2+) are presented. The coordination occurs within a few seconds, and the rate constant increases in the order Ni(2+) < Co(2+) < Fe(2+). With the rate constants at hand, the polymer growth of Ni-MEPE is computed.
We present a detailed study of metallo-supramolecular coordination polymers (MEPEs) and how to adjust their chain-length and viscosity. A model is established, which can easily be used to prepare MEPEs of desired average molecular weight.
Several transition metal ions, like Fe , Co , Ni , and Zn complex to the ditopic ligand 1,4-bis(2,2':6',2''-terpyridin-4'-yl)benzene (L). Due to the high association constant, metal-ion induced self-assembly of Fe , Co , and Ni leads to extended, rigid-rod like metallo-supramolecular coordination polyelectrolytes (MEPEs) even in aqueous solution. Here, we present the kinetics of growth of MEPEs. The species in solutions are analyzed by light scattering, viscometry and cryogenic transmission electron microscopy (cryo-TEM). At near-stoichiometric amounts of the reactants, we obtained high molar masses, which follow the order Ni-MEPE≈Co-MEPE
Metallosupramolekulare Koordinationspolyelektrolyte entstehen durch metallioneninduzierte Polymerisation von Bisterpyridinliganden. Über Konzentration der Edukte, pH‐Wert und Dauer der Polymerisation lassen sich die Kettenlängen einstellen. Zudem können Eigenschaften wie Selbstheilung und reversible Farbänderung implementiert werden.
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