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Aminotroponiminates as ligands for potential metal-based nitric oxide sensors.

Publication ,  Journal Article
Franz, KJ; Singh, N; Spingler, B; Lippard, SJ
Published in: Inorganic chemistry
September 2000

A family of new fluorescently labeled ligands, HRDATI, was prepared to develop transition-metal-based NO sensing strategies. The ligands are composed of aminotroponiminates (ATIs) with a dansyl fluorophore on one of the imine nitrogen atoms and an alkyl substituent, either i-Pr (8), t-Bu (9), or Bz (10), on the other. Bis(chelate) Co2+ ([Co(i-PrDATI)2] (12), [Co(t-BuDATI)2] (14), [Co(BzDATI)2] (15)) and Zn2+ ([Zn(i-PrDATI)2] (13)) complexes were prepared and characterized by X-ray crystallography. The bis(ATI) complex [Co(i-Pr2ATI)2] (11) was also prepared and its X-ray crystal structure determined. Cyclic voltammetry reveals reversible redox waves at -2.57 and -0.045 V (vs Cp2Fe/Cp2Fe+) in THF for the Co2+/Co+ and Co3+/Co2+ couples, respectively, of 11. Only a Co2+/Co+ wave at -2.09 V is observed for 12. When excited at 350 nm, the HRDATI ligands and the diamagnetic Zn2+ complex 13 fluoresce around 500 nm, whereas the paramagnetic Co2+ complexes quench the fluorescence. These air-stable cobalt compounds react with nitric oxide to dissociate a DATI ligand and form neutral dinitrosyl complexes, [Co(NO)2(RDATI)]. The release of the fluorophore-containing ligand is accompanied by an increase in fluorescence intensity, thus providing a strategy for fluorescent NO sensing. Linking two DATI moieties via a tetramethylene chain affords the ligand H2DATI-4 (18). The Co2+ complex [Co(DATI-4)] (19) reacts more readily with NO than the bis(DATI) compounds and also displays an increase in fluorescence intensity upon NO binding.

Duke Scholars

Published In

Inorganic chemistry

DOI

EISSN

1520-510X

ISSN

0020-1669

Publication Date

September 2000

Volume

39

Issue

18

Start / End Page

4081 / 4092

Related Subject Headings

  • Inorganic & Nuclear Chemistry
  • 3403 Macromolecular and materials chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0306 Physical Chemistry (incl. Structural)
  • 0302 Inorganic Chemistry
 

Citation

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Franz, K. J., Singh, N., Spingler, B., & Lippard, S. J. (2000). Aminotroponiminates as ligands for potential metal-based nitric oxide sensors. Inorganic Chemistry, 39(18), 4081–4092. https://doi.org/10.1021/ic000344q
Franz, K. J., N. Singh, B. Spingler, and S. J. Lippard. “Aminotroponiminates as ligands for potential metal-based nitric oxide sensors.Inorganic Chemistry 39, no. 18 (September 2000): 4081–92. https://doi.org/10.1021/ic000344q.
Franz KJ, Singh N, Spingler B, Lippard SJ. Aminotroponiminates as ligands for potential metal-based nitric oxide sensors. Inorganic chemistry. 2000 Sep;39(18):4081–92.
Franz, K. J., et al. “Aminotroponiminates as ligands for potential metal-based nitric oxide sensors.Inorganic Chemistry, vol. 39, no. 18, Sept. 2000, pp. 4081–92. Epmc, doi:10.1021/ic000344q.
Franz KJ, Singh N, Spingler B, Lippard SJ. Aminotroponiminates as ligands for potential metal-based nitric oxide sensors. Inorganic chemistry. 2000 Sep;39(18):4081–4092.
Journal cover image

Published In

Inorganic chemistry

DOI

EISSN

1520-510X

ISSN

0020-1669

Publication Date

September 2000

Volume

39

Issue

18

Start / End Page

4081 / 4092

Related Subject Headings

  • Inorganic & Nuclear Chemistry
  • 3403 Macromolecular and materials chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0306 Physical Chemistry (incl. Structural)
  • 0302 Inorganic Chemistry