Using eugenol scaffold to explore the explosive sensing properties of Cd(II)-based coordination polymers:...

Eugenol, the major constituent of clove oil, has been explored as an essential natural ingredient for ages owing to its versatile pharmacological properties. However, to date, the coordination chemistry of eugenol derivatives has not been much explored. In the present work, an eugenol-based Schiff base ligand (HL) was synthesized and structurally confirmed through ESI-MS, NMR, and FT-IR spectroscopy studies. Consequently, the N,O-donor chelating ligand HL was coordinated with Cd²⁺, in the presence of bridging pseudohalides (thiocyanate, SCN^-, and dicyanamide, N(CN)₂^-) to synthesize two luminescent coordination polymers (CPs 1 and 2): [Cd₂(L)₂(X)₂] (where HL = 4-allyl-2-(((2-(benzylamino)ethyl) imino)methyl)-6-methoxyphenol and Xs are bridging pseudohalides, i.e., SCN^- and N(CN)₂^-) on a Cd-eugenol scaffold. The CPs depicted structural diversity, bulk-phase purity, thermal stability, and the presence of interlayer supramolecular C-H⋯π interactions together with C-H⋯S (for CP 1) and C-H⋯N (for CP 2) interactions. The CPs further exemplified themselves as selective and sensitive 'turn-off' probes towards trinitrophenol (TNP) (quenching efficiency: 82.02% and 83.86% for 1 and 2) among a pool of hazardous nitroaromatic compounds (NACs). Accordingly, 1 and 2 exhibited an ultralow limit of detection (LOD) of 0.29 and 0.15 μM, with high quenching constants (K_SV) of 5.91 × 10⁴ and 17.60 × 10⁴ M^-1, respectively. In addition, TNP sensing events were evidenced to be recyclable and exhibited fast response (∼31 s, 1, and ∼40 s, 2), which increased its real-world viability. Vapor phase TNP sensing was also accomplished upon drop-casted CP films. Experimental investigations and theoretical DFT study confirmed the cooperative occurrence of RET-IFE-PET-collisional quenching and non-covalent π⋯π stacking as key factors involved in the TNP sensing performance. The competency of 1 and 2 in the detection of TNP from several complex environmental matrices (CEMs), viz. matchstick powder, river and sewage water, and soil specimens, was also established with good recovery (∼66-86% and ∼68-93% for 1 and 2, respectively) and high K_SV values (3.90-11.39 × 10⁴ and 6.17-18.79 × 10⁴ M^-1 for 1 and 2, respectively).