Second-Coordination-Sphere Assisted Selective Colorimetric Turn-on Fluoride Sensing by a Mono-Metallic Co(II) Hexacarboxamide Cryptand Complex
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Author(s)
Stauber, Julia M.
Alliger, Glen Edward
Nocera, Daniel G
Cummins, Christopher C
Date Issued
June 2017
Journal
Inorganic Chemistry
Publisher
American Chemistry Society
Citation
Stauber, Julia M., Glen E. Alliger, Daniel G. Nocera, and Christopher C. Cummins. “Second-Coordination-Sphere Assisted Selective Colorimetric Turn-on Fluoride Sensing by a Mono-Metallic Co(II) Hexacarboxamide Cryptand Complex.” Inorganic Chemistry 56, no. 14 (June 30, 2017): 7615–7619.
Version
Author's final manuscript
Abstract
The preparation of a selective turn-on colorimetric fluoride sensor was achieved through single cobalt(II) ion insertion into a macrobicyclic cryptand. Monometallic [Co(mBDCA-5t-H₃)]− (1) and [Zn(mBDCA-5t-H₃)]− (2) complexes were prepared in 74 and 84% yields, respectively. Structural characterization of 1 confirmed the presence of a proximal hydrogen-bonding network consisting of carboxamide N–H donors. The reaction of 1 with F– was accompanied by a distinct colorimetric turn-on response in mixed aqueous/organic media, and 1 was capable of selective fluoride sensing in the presence of large quantities of potentially competitive anions. Complex 1 represents a unique example of a fluoride sensor wherein selective F– binding takes place directly at a transition-metal center and induces a color change based upon metal-centered transitions. The metal(II) fluoride complexes [F⊂Co(mBDCA-5t-H₃)]²– (3) and [F⊂Zn(mBDCA-5t-H₃)]²– (4) were both fully characterized, including single crystal X-ray analyses. Fluoride binding is synergistic involving hydrogen-bond donors from the second-coordination sphere together with metal(II) ion complexation.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/acs.inorgchem.7b01335
