Relevance of pyridinylpyrazine bridged Cd(II) dimer for the trace detection of Al3+ and 4-nitroaniline in aqueous medium and electrical conductivity measurement
• Pyridyl-pyrazine bridging Cd(II) dimer with carboxylate cap from sulfosalicylic acid. • Emission of the dimer is quenched by Al 3+ and LOD is 0.1313 µM. • 4-Nitroaniline also quenches the emission of the dimer and LOD is 0.0272 µM. • The X-Ray structure of dimer shows the presence of free phenolic -OH that may be responsible the selection of analyte. • Band gap 3.20 eV insists to design Schottky device and the electrical conductivity is 2.01 × 10⁻⁶ S·m⁻¹ (dark) and 5.62 × 10⁻⁶ Sm⁻¹ (light). Polypyridine metal complexes serve as light sensitive semiconducting materials and also efficient, sensitive and selective chemosensors for the trace quantity detection of toxic ions and molecules. A Cd(II)-based coordination dimer, {[(HSSA) 2 Cd 2 (μ-tppz)(H₂O) 4 ]·H₂O.CH₃OH}, 1 , bridged by 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz), and end capping carboxylate-O,O chelation by sulfosalicylic acid (H₃SSA) acts as strongly emissive (λ em = 402 nm) material which is quenched by Al 3+ with a detection limit (LOD), 0.1313 µM and a Stern-Volmer constant (K sv ), 4.85 × 10⁴ M⁻¹ in methanol-water (1:40, v/v). In addition, the emission of 1 has also been quenched by 4-nitroaniline (4-NA) in methanol-aqueous solution, a precursor to nitroaromatic dyes, even in the existence of other nitroaromatic compounds (ten NACs) and the LOD and K sv are 0.0272 µM and 5.04 × 10 5 M⁻¹ respectively. The quenching has been explained by the FRET and PET pathway. The presence of free phenolic-OH of HSSA²⁻ within the network may assist to invite selectively the analyte (Al 3+ and 4-NA) which may facilitate dissociation, promote energy transfer and contribute to the quenching effect. The compound, 1 , shows band gap 3.20 eV (theoretical, 3.31 eV) and may serve as semiconductor to fabricate Schottky diode device. The thin film of 1 was used to measure the electrical conductivity, 2.01 × 10⁻⁶ Sm⁻¹ at ambient condition which has been improved by light irradiation to 5.62 × 10⁻⁶ Sm⁻¹. Thus, stimulation by light underscores the possibility of this material for dual sensing applications and Schottky diode behaviour.
Authors
- Dipankar Sahoo (ORCID: https://orcid.org/0000-0003-4822-4444)
- S. Jana (ORCID: https://orcid.org/0000-0001-5772-7022)
- Koushik Saha (ORCID: https://orcid.org/0000-0002-8371-8952)
- Chittaranjan Sinha (ORCID: https://orcid.org/0000-0002-4537-0609)
- Sudip Kumar Naskar (ORCID: https://orcid.org/0000-0003-1588-4665)
- Narayan Ch. Jana (ORCID: https://orcid.org/0000-0002-2849-5784)
- Malabika Banerjee (ORCID: https://orcid.org/0000-0002-3921-4781)
- Indrajit Saha (ORCID: https://orcid.org/0000-0003-1438-8424)
Institutions
- Indian Institute of Science Education and Research Kolkata (IN)
- Jadavpur University (IN)
- Ramakrishna Mission Vidyamandira (IN)
- Ramakrishna Mission Vivekananda Educational and Research Institute (IN)
- Pan-European University (SK)
Publication Details
- Journal
- Journal of Molecular Structure
- Published
- 2025-09-02
- DOI
- https://doi.org/10.1016/j.molstruc.2025.143861
- Primary Topic
- Molecular Sensors and Ion Detection
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Council of Scientific and Industrial Research, India
- Human Resource Development Group
- Science and Engineering Research Board
- Rashtriya Uchchatar Shiksha Abhiyan