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Ferrocenyl Dithiophosphonate Stabilized Heterobimetallic (CoII/FeII, NiII/FeII, and CuI/FeII) Complexes: Synthesis,
Dilip Kumar Jangid1, Priti Kumari1, Saptarshi Ghosh Dastider2
1Department of Chemistry, Central University of Punjab, Bathinda 151401, India.
Abstract:
Ferrocenyl dithiophosphonate metal-based molecular compounds are infrequent with untapped potential in electrocatalysis and luminescence. A stoichiometric reaction of late 3d metal(II) (Co, Ni, Cu) salts with ferrocenyl dithiophosphonate NH4[S2P(OnPr)Fc] in a 1:2 ratio produces mononuclear [M{S2P(OnPr)Fc}2] {M = CoII (1), NiII (2)} complexes and a tetranuclear [Cu4{S2P(OnPr)Fc}4] (3) {Fc = Fe(η5-C5H4)(η5-C5H5)} cluster. The distinct core of 3 compared to 1 and 2 indicates that NH4[S2P(OnPr)Fc] first serves as a sacrificial reductant and subsequently stabilizes the Cu(I) cluster. Heterometallic species (1-3) were characterized by NMR (1H, 31P), FT-IR, TGA, UV-visible spectroscopy, ESI-MS, XPS, and single-crystal X-ray diffraction. Ligand [S2P(OnPr)Fc]- stabilized the redox-derived tetrahedral CuI core of 3 and the M(II)-centered square (MS4) frame in 1 and 2 through (η3; μ1, μ2) and (η; μ1, μ1) bonding patterns, respectively. The irreversible single wave voltammogram indicated nonuniform electrochemical behavior of 1-3. TD-DFT indicates MLCT and weak LLCT in isostructural 1-2 and 3m [CuII{S2P(OnPr)Fc}2], while 3 exhibits multielectron transitions with two types of MLCT. Third-order decay confirms singlet fluorescence, and multiple electronic transitions in 3 enhance its photoluminescence (27.5% QY) relative to 1-2, correlating the isostructural and different nuclearity features of late 3d metals with their physical and electrochemical properties.
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