Peripheral metal-ion binding to tris(thia-oxo crown) porphyrazines

We report the preparation and solution properties of metal-free [1b(H(2))] and cobalt [1c(Co)] porphyrazines (pz's), where three pyrroles are functionalized with a S(2)O(3) crown ether for metal-ion binding and the fourth pyrrole is appended with two long-chain alcohols (bis((11-hydroxyundecyl)thio)) for potential use as surface anchors. Compounds 1b(H(2) and 1c(Co) exhibit ion-specific optical changes in the presence of Ag(+) and Hg(2+). Binding of Ag(+) to 1b(H(2)) is described by a 1:1 binding isotherm, with K(D) approximately 147 microM, whereas binding of Hg(2+) to 1b(H(2)) appears more complex. For 1c(Co), binding of Ag(+) and Hg(2+) also can be fit to a 1:1 isotherm, with K(D) approximately 109 and 83 microM, respectively. All four titrations show nonisosbesticity, including those apparently describable by the 1:1 isotherm, which indicates that there are intermediate stages as multiple ions bind. Neither 1b(H(2)) or 1c(Co) gives optical responses to Ni(2+), Zn(2+), Pb(2+), or Cu(2+) or to alkali (Li(+), Na(+), K(+), and Cs(+)) and alkaline earth (Mg(2+), Ca(2+), and Ba(2+)) metal ions. Nonetheless, "hard" ions are sensed electrochemically: Na(+) and Li(+) strongly shift the pz/pz(-) couple of 1b(H(2)()) and Co(III)/Co(II) couple of 1c(Co). For the addition of 4 equiv of Li(+) to 1c(Co), the Co(III)/Co(II) shifts +40 mV, and for the addition of 4 equiv of Na(+) to 1c(Co), the shift is +155 mV. The shifted redox waves of 1c(Co) all retain their reversibility. In contrast, for the addition of either 4 equiv of Li(+) or Na(+) to 1b(H(2)), the shifts of the pz/pz(-) couple are essentially the same, approximately 170 mV, and the shifted redox waves become broadened and less reversible, due to ion-induced aggregation. For 1c(Co) the shape of the titration curves [M]/[1b(H(2))] versus E(1/2) is concave to the x-axis, implying cooperative binding of multiple M(+) ions as part of the redox/binding system of equilibria.