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Achieving Selectivity for Copper over Zinc with Luminescent Terbium Probes Bearing Phenanthridine Antennas

Abstract

A family of terbium probes was synthesized and evaluated for the luminescent detection of copper and zinc in water at neutral pH. Each probe incorporates a terbium ion chelated by a macrocyclic polyaminocarboxylate and conjugated to either one, two, or three phenanthridine antennas via a diamine linker. All three probes, Tb-1Phen, Tb-2Phen, and Tb-3Phen, exhibit similar responses toward copper and zinc. In each case, the terbium-centered time-gated phosphorescence decreases upon binding either CuI or CuII but not upon addition of ZnII. The phosphorescence of Tb-2Phen is also not significantly affected by other metal ions including MgII, CaII, MnII, FeII, NiII, CdII, or HgII Tb-1Phen, on the other hand, responds weakly to MnII, FeII and NiII. The lack of affinity of each probe for ZnII was further confirmed by competition experiments with CuI and CuII. Notably, whereas the terbium-centered emission of each probe is quenched upon copper coordination, the phenanthridine-centered luminescence emission is not. As such, each probe functions as a ratiometric probe for the selective detection of copper over zinc. Theoretical calculations further demonstrate that the turn off response of the probe is due to an increase in distance separating the lanthanide ion from its phenanthridine antenna upon coordination of copper, which in turn decreases the efficiency of terbium sensitization by the phenanthridines.

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Publication details

The article was received on 07 Nov 2017, accepted on 10 Jan 2018 and first published on 11 Jan 2018


Article type: Paper
DOI: 10.1039/C7DT04203E
Citation: Dalton Trans., 2018, Accepted Manuscript
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    Achieving Selectivity for Copper over Zinc with Luminescent Terbium Probes Bearing Phenanthridine Antennas

    K. Srivastava, S. Harris, A. League, K. Ziebarth and V. Pierre, Dalton Trans., 2018, Accepted Manuscript , DOI: 10.1039/C7DT04203E

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