Journal
INORGANIC CHEMISTRY
Volume 51, Issue 21, Pages 11315-11323Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic3004504
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- Chemical Sciences, Geosciences and Biosciences Division of the Office of Basic Energy Sciences of the U.S. Department of Energy [DE-FG02-08ER15986]
- U.S. Department of Energy (DOE) [DE-FG02-08ER15986] Funding Source: U.S. Department of Energy (DOE)
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An artificial peptide with three pendant hydroxyquinoline (hq) ligands on a palindromic backbone was designed and used to form multimetallic assemblies. Reaction of the tripeptide with zinc acetate led to a highly fluorescent tripeptide duplex with three Zn(II) coordinative cross-links. The binding process was monitored using spectrophotometric absorbance and emission titrations; NMR spectroscopy and mass spectrometry confirmed the identity and stoichiometry of the product structure. Titrations monitoring duplex formation of the zinc-tripeptide structure had a sigmoidal shape, equilibrium constant larger than the monomeric analogue, and a Hill coefficient >1, all of which indicate positive cooperativity. Photophysical characterization of the quantum yield, excited state lifetime, and polarization anisotropy are compared with the monometallic zinc-hq analogue. A higher than expected quantum yield for the trimetallic complex suggests a structure in which the central chromophore is shielded from solvent by it-stacking with neighboring Zn(II) complexes.
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