Fluorescent and electrochemical sensing of polyphosphate nucleotides by ferrocene functionalised with two Zn(II)(TACN)(pyrene) complexes

Chemistry : a European Journal
Zhanghua ZengLeone Spiccia

Abstract

The [Fc-bis{Zn(II)(TACN)(Py)}] complex, comprising two Zn(II)(TACN) ligands (Fc=ferrocene; Py=pyrene; TACN=1,4,7-triazacyclononane) bearing fluorescent pyrene chromophores linked by an electrochemically active ferrocene molecule has been synthesised in high yield through a multistep procedure. In the absence of the polyphosphate guest molecules, very weak excimer emission was observed, indicating that the two pyrene-bearing Zn(II)(TACN) units are arranged in a trans-like configuration with respect to the ferrocene bridging unit. Binding of a variety of polyphosphate anionic guests (PPi and nucleotides di- and triphosphate) promotes the interaction between pyrene units and results in an enhancement in excimer emission. Investigations of phosphate binding by (31)P NMR spectroscopy, fluorescence and electrochemical techniques confirmed a 1:1 stoichiometry for the binding of PPi and nucleotide polyphosphate anions to the bis(Zn(II)(TACN)) moiety of [Fc-bis{Zn(II)(TACN)(Py)}] and indicated that binding induces a trans to cis configuration rearrangement of the bis(Zn(II)(TACN)) complexes that is responsible for the enhancement of the pyrene excimer emission. Pyrophosphate was concluded to have the strongest affinity to [Fc-bis{Zn(II)...Continue Reading

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Apr 8, 2014·Journal of Fluorescence·Bishwapran KashyapProdeep Phukan
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