Synthesis, characterization and multi-dimensional application approach for two distinctive tetra nuclear, first-time reported, Fe3+/Hg2+ and Fe3+/Cd2+ clusters from a new Fe3+ containing metalloligand

• Published in: New journal of chemistry 2022-09, Vol.46 (35), p.16730-16742
• Main Authors: Laha, Soumik, Sathapathi, Dibyendu, Das, Mainak, Das, Manik, Ray, Partha Pratim, Bag, Arijit, Samanta, Bidhan Chandra, Das, Uttam Kumar, Maity, Tithi
• Format: Article
• Language: English
• Subjects: Aqueous solutions; Cadmium; Clusters; Data analysis; Dyes; Effectiveness; Energy gap; Energy value; Ethane; Ferric ions; Hydrogen peroxide; Imines; Inspection; Light irradiation; Mercury (metal); Methylene blue; Photodegradation; Single crystals; Transition metals
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/d2nj03357g

A new mononuclear Fe3+ metalloligand MC1 [FeLN3(H2O)], developed by using the N2O2 donor Schiff base ligand H2L, has been successfully used to detect and remove Hg2+ and Cd2+ from several transition metal ions with the formation of two unusual hetero metallic μ-oxo Fe3+–Hg2+/Cd2+ clusters, [(Fe23+)(μ-O)L2Cl4(Hg22+)] (MC2) and [(Fe23+)(μ-O)L2I4Cd22+] (MC3) [(where H2L is 6, 6′-(1E, 1′E) (ethane-1, 2 diylbis(azaneylidene))bis(methaneylylidene))bis(2-ethoxyphenol)]. All three complexes were identified by X-ray single-crystal data analysis along with a range of spectral studies. In MC1, the Fe3+ is coordinated with deprotonated H2L, one water molecule, and one azide ion as a secondary anionic residue, forming an octahedral geometry. Interestingly, MC2 and MC3 are isostructural, where each asymmetric unit contains deprotonated H2L, one Fe3+ and Hg2+/Cd2+ metal center, two Cl−/I− and two Fe3+ centers are connected by a μ-O bridge to form tetranuclear complexes. As the band gap energy values of MC1, MC2, and MC3 (3.07 eV, 2.69 eV, and 2.55 eV, respectively) are in the visible region so all the three complexes are exposed to investigate their potentiality to be effective Schottky devices and at the same time a thorough inspection has been carried out to check their catalytic behaviour in aqueous medium in terms of methylene blue (MEB) dye degradation under visible light irradiation. A thorough inspection reveals the better MB dye degradation potentiality of MC3 in comparison to MC2 in the presence of H2O2. At the same time, the investigation of the device performances, conductivity, and device parameters disclose more effectiveness of MC3 in comparison to MC2 in a better Schottky device. The effectiveness of MC3 in both applications may be attributed to its lower band gap value.