This critical review focuses on the development of photochromic compounds as sensors for cations, anions, and biologically important molecules. The review commences with a brief description of photochromism and the strategies to exploit photochromic molecular switches' properties for sensing application. This is followed by a summary of photoswitchable receptors emerged to date and classified according to the photochromic structure they are based on. These include azobenzenes, fulgides, dithienylethenes, dihydroindolizines, chromenes and spiropyrans.

The design, synthesis and complete characterization of a smart material composed of the merocyanine open form. We were also able to provide the first example of a continuous solution based on-off switching in a spiropyran-nanotube material.

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 ZnCl(2) and Zn(ClO(4))(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 x 10(-7) M for Zn(ClO(4))(2). The counterion also influences binding constants and the equilibrium constants for Cu(ClO(4))(2) and CuCl(2) are K = 3.37 x 10(4) M(-1) to K = 2.04 x 10(3) 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'.

Please cite this article as: Natali M, Soldi L, Giordani S. A photoswitchable Zn (II) selective spiropyranbased sensor, Tetrahedron (2010Tetrahedron ( ), doi: 10.1016Tetrahedron ( /j.tet.2010 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

A series of four spiropyrans bearing different substituents on the indolic nitrogen were synthesized and their capability of binding mono and bivalent transition metal cations in solution was assessed via UV-visible absorption spectroscopy. All the compounds responded selectively to the presence of Cu(II) ions producing intense absorption bands in the visible region of their spectra. Bidimensional 1 H-NMR and MALDI-TOF MS spectroscopies revealed the formation of SP dimers mediated by Cu(II). This is the first example of cross-coupling mediated by copper(II) in mild conditions causing the symmetric dimerization of spiropyran dyes.