Synthesis of a trinuclear zinc(ii) cluster composed of [4.4.3.01,5]tridecane cages: a rapid detection and degradation probe for the chemical warfare agent simulant diethyl cyanophosphonate in protein-rich food products

Abstract

Diethyl cyanophosphonate (DCNP), a simulant of Tabun, is a common pollutant in pharmaceutical waste and poses a high risk to living organisms. Herein, we demonstrate a compartmental ligand-derived trinuclear zinc(II) cluster [Zn₃(LH)₂(CH₃COO)₂] as a probe for the selective detection and degradation of DCNP. It consists of two pentacoordinated Zn(II) [4.4.3.0^1,5]tridecane cages bridged through a hexacoordinated Zn(II) acetate unit. The structure of the cluster has been elucidated by spectrometric, spectroscopic, and single-crystal X-ray diffraction studies. The cluster shows a two-fold increased emission as compared to the compartmental ligand (at λ_exc = 370 nm and λ_em = 463 nm) due to the chelation-enhanced fluorescence effect and acts as a turn-off signal in the presence of DCNP. It can detect DCNP at nano levels up to 186 nM (LOD). The direct bond formation between DCNP and Zn(II) via the –CN group degrades it to inorganic phosphates. The mechanism of the interaction and degradation is supported by spectrofluorimetric experiments, NMR titration (¹H and ³¹P), time of flight mass spectrometry and density functional theory calculations. The applicability of the probe has been further tested by the bio-imaging of zebrafish larvae, analysis of high-protein food products (meat and fish) and vapour phase detection by paper strips.