Discerning the detection of 2,4,6-trinitrophenol (TNP)-like
mutagenic
pollutants and other nitroaromatic-based explosives (NACs) using robust
luminescent metal complexes has been always a potential research field.
Herein, we report the synthesis of three novel luminescent chloro-bridged
heavy metal complexes of formulation [M2(HL)2Cl4] where M stands for Zn2+,
Cd2+, and Hg2+ for complexes 1, 2, and 3, respectively, by refluxing the mixture
of ligand HL and metal chloride salts. Single-crystal
X-ray study, spectroscopic (1H NMR, FT-IR, UV–vis,
and emission spectroscopy) techniques, DFT, and TDDFT calculations
have all been used to fully characterize the complexes. All the three
complexes exhibit excellent fluorescence responses which get quenched
in the presence of different NACs. Interestingly, the fluoroprobes
(1–3) are more selective and sensitive
toward TNP over several other comparative NACs with high (in the order
of ∼104 M–1) quenching constants
(K
SV) and nanomolar detection limit (LOD),
and complex-coated TLC plates were used to detect TNP in the solid
state. Moreover, our probes were quite sensitive for the trace detection
of TNP in real samples. Among the three, complex 3 is
the most efficacious with K
SV (5.19 ±
0.12) × 104 M–1 and LOD of 180.2
nM. 1H NMR and fluorescence lifetime titration of probes
with TNP shed light on the nature of the interaction (dynamic quenching)
of probes with TNP. In addition, DFT and UV–vis absorption
of probes with TNP proved that the quenching phenomenon could be primarily
ascribed to photo-induced electron transfer (PET) and resonance energy
transfer (RET).