Issue 39, 2023

Controlling the sensitivity and selectivity for the detection of nitro-based explosives by modulating the electronic substituents on the ligand of AIPE-active cyclometalated iridium(iii) complexes

Abstract

Nitroaromatic compounds are extremely explosive materials that pose a national security risk and raise environmental concerns. The design and development of sensitive and selective compounds for explosive materials are highly desirable. ‘Aggregation-Induced Emission’ (AIE) active materials are best suited for sensing purposes because of their sensitivity, fast detection time, and easy operation. By rationally incorporating substituents on the cyclometalated (C^N) ligand, four different AIE active iridium(III) based monocyclometalated complexes with the general formula [Ir(PPh3)2(H)(Cl)(C^N)] were synthesized. The phenyl ring of the phenyl pyridine cyclometalated portion of an iridium(III) complex was substituted with the right substituents to adjust the FMO levels thus, leading to appropriate alignment of the energy levels. Each of the resulting complexes displayed a significant property known as ‘Aggregation-Induced Phosphorescent Emission’ (AIPE). The complexes were subjected to structural characterization, electrochemical analysis, and photophysical property studies. The synthesized complexes were employed for the detection of aromatic nitro explosive compounds such as trinitrophenol (TNP) and trinitrotoluene (TNT) in the aqueous phase with a high degree of sensitivity. The sensing capabilities of each complex were assessed for these nitro explosive compounds and compared to those of the unsubstituted iridium(III) complex (M). Notably, the best limits of detection for TNP and TNT have been achieved with iridium(III) complexes [M1 (489 pM) and M3 (3.6 nM)] within the literature reported until now. For detecting picric acid with M1, FRET was found to be the potential mechanism, and for TNT, PET was found to be the cause of emission quenching by M3. Furthermore, for low-cost detection, filter paper-based sensing was also found effective for each complex. Real-field sensing of PA in soil samples was also performed.

Graphical abstract: Controlling the sensitivity and selectivity for the detection of nitro-based explosives by modulating the electronic substituents on the ligand of AIPE-active cyclometalated iridium(iii) complexes

Supplementary files

Article information

Article type
Paper
Submitted
12 7 2023
Accepted
07 9 2023
First published
08 9 2023

Dalton Trans., 2023,52, 14182-14193

Controlling the sensitivity and selectivity for the detection of nitro-based explosives by modulating the electronic substituents on the ligand of AIPE-active cyclometalated iridium(III) complexes

A. Agarwal, R. P. Bhatta, V. Kachwal and I. R. Laskar, Dalton Trans., 2023, 52, 14182 DOI: 10.1039/D3DT02198J

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