Issue 35, 2010

The role of metal ions and counterions in the switching behavior of a carboxylic acid functionalized spiropyran

Abstract

The ability of a carboxylic acid functionalized spiropyran, SP, to act as a reversible and selective receptor for metal ions has been systematically examined. A series of spectroscopic measurements, combined with single-crystal X-ray diffraction have been employed in order to determine metal-ion sensitivity and selectivity, binding constants, solution compositions, binding kinetics as well as solid-state structure of a metal-complex of this ligand. This molecule acts as a chelating ligand and binds to metal ions using a triad of functionalities and will release the metal ion by application of visible light. Altering the complex from ZnCl2 and Zn(ClO4)2, leads to only a small change in the complex absorption maxima from 494 to 492 nm, but produced a drastic increase in the sensitivity for the zinc(II) ion. Fluorescence spectroscopy was employed to establish that the detection limit for Zn(II) is approximately 3 × 10−7 M for Zn(ClO4)2. The counterion also influences binding constants and the equilibrium constants for Cu(ClO4)2 and CuCl2 are K = 3.37 × 104 M−1 to K = 2.04 × 103 M−1, respectively. Additionally, in the presence of perchlorate, the spiropyran-Cu complex formation is fast enough to allow for real-time naked eye detection of this metal ion in less than three minutes; the formation of other metal complexes takes between 50 minutes to 2 hours. Finally, the single-crystal structure determination of the SP-zinc chloride complex shows that the Zn(II) ion displays a distorted square-pyramidal arrangement, and neighbouring metal ions are bound together into a 1-D coordination polymer with a hydrophilic core, surrounded by hydrophobic ‘cladding’.

Graphical abstract: The role of metal ions and counterions in the switching behavior of a carboxylic acid functionalized spiropyran

Supplementary files

Article information

Article type
Paper
Submitted
31 Mar 2010
Accepted
22 Jun 2010
First published
06 Aug 2010

Dalton Trans., 2010,39, 8269-8277

The role of metal ions and counterions in the switching behavior of a carboxylic acid functionalized spiropyran

M. Natali, C. Aakeröy, J. Desper and S. Giordani, Dalton Trans., 2010, 39, 8269 DOI: 10.1039/C0DT00242A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements