Prodigiosin analogue designed for metal coordination: Stable zinc and copper pyrrolyldipyrrins

Tsuhen M. Chang, Sanhita Sinharay, Andrei V. Astashkin, Elisa Tomat

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

The pyrrolyldipyrrin motif is found in several naturally occurring prodigiosin pigments. The potential roles of the interactions of prodigiosins with transition metals and the properties of metal-bound pyrrolyldipyrrins, however, have been difficult to assess because of the very limited number of well-characterized stable complexes. Here, we show that the introduction of a meso-aryl substituent and an ethyl ester group during the sequential assembly of the three heterocycles affords a pyrrolyldipyrrin of enhanced coordinating abilities when compared to that of natural prodigiosins. UV-visible absorption studies indicate that this ligand promptly binds Zn(II) ions with 2:1 ligand-to-metal stoichiometry and Cu(II) ions with 1:1 stoichiometry. Notably, no addition of base is required for the formation of the resulting stable complexes. The crystal structures reveal that whereas the tetrahedral zinc center engages two nitrogen donors on each ligand, the pseudosquare planar copper complex features coordination of all three pyrrolic nitrogen atoms and employs the ester group as a neutral ligand. This first example of coordination of a redox-active transition metal within a fully conjugated pyrrolyldipyrrin framework was investigated spectroscopically by electron paramagnetic resonance to show that the 1:1 metal-to-ligand ratio found in the crystal structure is also maintained in solution.

Original languageEnglish (US)
Pages (from-to)7518-7526
Number of pages9
JournalInorganic Chemistry
Volume53
Issue number14
DOIs
StatePublished - Jul 21 2014

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Prodigiosin
Zinc
Copper
zinc
Metals
analogs
Ligands
copper
ligands
metals
Stoichiometry
Transition metals
esters
stoichiometry
Esters
Nitrogen
Crystal structure
transition metals
Ions
crystal structure

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Medicine(all)

Cite this

Prodigiosin analogue designed for metal coordination : Stable zinc and copper pyrrolyldipyrrins. / Chang, Tsuhen M.; Sinharay, Sanhita; Astashkin, Andrei V.; Tomat, Elisa.

In: Inorganic Chemistry, Vol. 53, No. 14, 21.07.2014, p. 7518-7526.

Research output: Contribution to journalArticle

Chang, Tsuhen M. ; Sinharay, Sanhita ; Astashkin, Andrei V. ; Tomat, Elisa. / Prodigiosin analogue designed for metal coordination : Stable zinc and copper pyrrolyldipyrrins. In: Inorganic Chemistry. 2014 ; Vol. 53, No. 14. pp. 7518-7526.
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