High-fidelity detection of picric acid following proton prompted fluorescence quenching by a novel acridine yellow G-based binuclear ZnII-metallacycle

• Published in: New journal of chemistry 2024-06, Vol.48 (25), p.11530-11541
• Main Authors: Chand, Prem, Kumar, Ashish
• Format: Article
• Language: English
• Subjects: Aromatic compounds; Chemical bonds; Energy transfer; Fluorescence; Ground state; Imines; Ion pairs; Liquid phases; NMR; Nuclear magnetic resonance; Organometallic compounds; Quenching; Single crystals; Solid phases
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/d3nj05688k

Synthesis of a highly fluorescent binuclear ZnII-metallacycle (1) based on a novel Schiff base (H2L) viz. 2,7-dimethylacridine-3,6-diyl-bis(azaneylylidene)-bis(methaneylylidene)-bis(3-diethylaminophenol) is described and characterized through various spectral (FT-IR, 1H-NMR and HRMS) methods followed by structural authentication of 1 by single crystal X-ray diffraction analysis. The ZnII-metallacycle 1 is strategically incorporated with four –N(C2H5)2 groups, which enables it to exhibit excellent selectivity towards picric acid (PA) among other nitro aromatic compounds (NACs) in the form of fluorescence quenching (71%). The vital role of –N(C2H5)2 is substantiated by performing UV-vis, fluorescence, and 1H-NMR spectral and DFT studies on 1 with all NACs and comparing it with a model complex 2, which lacks the –N(C2H5)2 group. Studies revealed that the quenching involved a static and dynamic mechanism with a quenching constant (KSV) of 3.44 × 104 M and LOD of 7.62 × 10−8 M. The static pathway involved the formation of a H-bonded ground state ion pair complex of 1 and PA [1-(C2H5)2N–H+⋯O−–picrate] and the dynamic quenching is attributed to energy transfer from the excited state of 1 to the ground state of PA facilitating polar–polar resonance between them. Conclusively, 1 has been demonstrated as a significant probe, which can be employed for naked eye detection of PA in solid and liquid phases.