Synthesis, characterization, crystal structure and DFT studies of a palladium(II) complex with an asymmetric Schiff base ligand

The template‐free synthesis and the characterization of an active electrocatalyst are performed for both the hydrogen evolution and oxygen reduction reactions in acidic media. In this work, the unique chelation mode of benzene‐1,4‐dithiocarboxamide (BDCA) is first used to synthesize a novel palladium‐BDCA coordination polymer (PdBDCA) as a precursor of palladium sulfide nanoparticles‐decorated nitrogen and sulfur doped carbon (Pd4S‐SNC). The newly synthesized PdBDCA and Pd4S‐SNC nanoparticles are characterized using chemical, electrochemical, and surface analysis methods. Notably, the nanoparticles obtained at 700 °C exhibit the remarkable catalytic property for the hydrogen evolution reaction in 0.5 m H2SO4, showing the overpotential of 32 mV (vs reversible hydrogen electrode (RHE)) and Tafel slope of 52 mV dec−1, which are comparable to that of Pt/C. The catalyst also shows a high oxygen reduction activity, offering the half‐wave and onset potentials of 0.92 and 0.77 V (vs RHE) in 0.5 m H2SO4, with improved methanol tolerance and long‐term stability compared with Pt/C. The present study gives a way for the design of excellent electrocatalyst for the energy conversion devices in the corrosive acidic environment.

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“…The def2‐TZVPD basis set was selected for the palladium, sulfur atom, and LANL2DZ was used for the other atoms. [ 33 ]…”

Section: Methodsmentioning

confidence: 99%

Hydrogen Evolution and Oxygen Reduction Reactions in Acidic Media Catalyzed by Pd₄S Decorated N/S Doped Carbon Derived from Pd Coordination Polymer

Huang

Seo

Park

et al. 2021

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“…1 E g with the square planar environment around Pd ions in complexes. [44,45] The optical energy gap of metal complexes is evaluated from the absorption spectra. Tauc's equation (Equation 1) helps in deciding the optical energy gap of complexes represented as below [46,47] :…”

Section: Electronic and Magnetic Studiesmentioning

confidence: 99%

Synthesis, spectroscopic, theoretical and biological evaluation of novel Schiff base complexes of divalent transition metals

Singh

Siwach

2021

Applied Organom Chemis

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In the present manuscript, a new series of triazole-based Schiff base, (E)-4-((3-fluoro-4-methoxybenzylidene)amino)-5-propyl-4H-1,2,4-triazole-3-thiol (FMBT) and its metal complexes with divalent cobalt, nickel, copper, zinc and palladium are prepared and investigated for biological activities. The structural assignments of all the synthesized ligand and its metal complexes were done using different spectral methods like mass, infrared (IR), 1 H-NMR, elemental analysis, electron spin resonance (ESR) and ultraviolet (UV)-visible. The magnetic properties, fluorescence profile and redox (cyclic voltammetry) behaviour of all the complexes were also investigated. Based on the spectral studies, the octahedral (Co[II], Ni[II] and Zn[II]) and square planar (Cu[II] and Pd[II]) structural environment have been proposed to the metal complexes. The results obtained from thermal and IR data confirmed the presence of coordinated water in metal complexes. The conductance measurements confirmed the non-electrolytic nature of metal complexes. Density functional theory (DFT)-based methods were used to ascertain the stability and chemical inertness of the compounds. Various electrostatic properties were also investigated by utilising the value of energy associated with different frontier molecular orbitals. The decomposition behaviour and stability of all the metal complexes was established from different thermodynamical functions calculated usingCoats-Redfern method. The bio-efficacy of bidentate ligand and its complexes was evaluated against a wide spectrum of microbial cultures using Broths dilution method. Among the novel metal complexes Ni (1:2) (minimum inhibitory concentration [MIC] = 62.5 μg ml À1 ), Cu (1:1) (MIC = 62.5 μg ml À1 ) and Zn (1:2) (MIC = 12.5 μg ml À1 ) complexes were found to be more potent against Escherichia coli than the standard drugs.

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“…The reactivity of the metal complexes can also be measured by density functional theory (DFT) studies to find the electron affinities, ionization potential and measurements 20,21 of orbital energies. The DFT studies can also be helpful to determine the relationship between bond length and strength of the N/O‐coordinating atoms with copper and zinc atoms, 22 whereas in recent years a lot of work has been reported on the synthesis and computational studies of Schiff base derived metal complexes 23–26 …”

Section: Introductionmentioning

confidence: 99%

“…The DFT studies can also be helpful to determine the relationship between bond length and strength of the N/O-coordinating atoms with copper and zinc atoms, 22 whereas in recent years a lot of work has been reported on the synthesis and computational studies of Schiff base derived metal complexes. [23][24][25][26] In continuation of previous research for the syntheses of metal complexes 4,[27][28][29][30][31][32][33][34] herein, we have synthesized a sulfonamide functionalized Schiff base ligand, that is, 2,4-dibromo-6-{[2-(1,1-dioxo-1H-benzoisothiazole-3-ylamino)-ethylimino]-methyl}-phenol.…”

mentioning

confidence: 99%

Sulfonamide derived Schiff base Mn (II), Co (II), and Ni (II) complexes: Crystal structures, density functional theory and Hirshfeld surface analysis

Shehnaz

Siddiqui

Ashraf

et al. 2023

Applied Organom Chemis

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The three transition metal complexes of the ligand named as 2,4‐dibromo‐6‐{[2‐(1,1‐dioxo‐1H‐benzoisothiazole‐3‐yl‐amino)‐ethylimino]‐methyl}‐phenol 3 were synthesized with divalent manganese, cobalt and nickel metal ions and characterized by employing different analytical methods including UV–visible, FT‐IR and elemental analyses. The crystal structures of Mn (II) complex 4, Co (II) complex 5, and Ni (II) complex 6 are determined by single beam X‐rays crystallography, which confirm the distorted octahedral coordination of the complexes 4–6. The non‐covalent interactions of the complexes 4–6 are investigated by the Hirshfeld surface analysis. The tendency of the pair of chemical species to form crystal packing interactions are computed, which provide the favorable contacts in the crystal packing for the complexes 4–6. For the sake of computing strength of the crystal packing, void analysis is performed for the complexes 4–6. The non‐electrolytic nature of synthesized metal complexes was confirmed by molar conductance. The spectral analyses suggested that sulfonamide functionalized Schiff base behaves as bidentate ligand and coordinates with the metal center through phenolic oxygen and iminic nitrogen atoms. The density functional theory (DFT) studies were performed for the Mn (II), Co (II), and Ni (II) metal complexes at the B3LYP/LANL2DZ level of theory. The structural characteristics, vibrational analysis (IR), NMR analysis, UV–Vis, natural bonding orbital (NBO), frontier molecular orbital (FMO), charges (Mulliken and NPA), global reactivity descriptors, molecular electrostatic potential (MEP), and dipole moments were investigated using this method. The large values of stabilization energy, that is, 12.02, 15.25, and 23.81 kcal/mol were found for the complexes Mn (II) 4, Co (II) 5, and Ni (II) 6, respectively by NBO analysis. The global reactivity findings suggested the positive values of electron affinity for all complexes, which indicate the involvement of charge transfer reaction. Among these complexes, complex 6 is the most stable and complex 4 is the least. Further, FMO analysis indicated large HOMO‐LUMO gap (3.85–3.97 eV) with higher LUMO values for all metal complexes.

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Synthesis, characterization, crystal structure and DFT studies of a palladium(II) complex with an asymmetric Schiff base ligand

Cited by 46 publications

References 30 publications

Hydrogen Evolution and Oxygen Reduction Reactions in Acidic Media Catalyzed by Pd₄S Decorated N/S Doped Carbon Derived from Pd Coordination Polymer

Hydrogen Evolution and Oxygen Reduction Reactions in Acidic Media Catalyzed by Pd₄S Decorated N/S Doped Carbon Derived from Pd Coordination Polymer

Synthesis, spectroscopic, theoretical and biological evaluation of novel Schiff base complexes of divalent transition metals

Sulfonamide derived Schiff base Mn (II), Co (II), and Ni (II) complexes: Crystal structures, density functional theory and Hirshfeld surface analysis

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Synthesis, characterization, crystal structure and DFT studies of a palladium(II) complex with an asymmetric Schiff base ligand

Cited by 46 publications

References 30 publications

Hydrogen Evolution and Oxygen Reduction Reactions in Acidic Media Catalyzed by Pd4S Decorated N/S Doped Carbon Derived from Pd Coordination Polymer

Hydrogen Evolution and Oxygen Reduction Reactions in Acidic Media Catalyzed by Pd4S Decorated N/S Doped Carbon Derived from Pd Coordination Polymer

Synthesis, spectroscopic, theoretical and biological evaluation of novel Schiff base complexes of divalent transition metals

Sulfonamide derived Schiff base Mn (II), Co (II), and Ni (II) complexes: Crystal structures, density functional theory and Hirshfeld surface analysis

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Product

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Hydrogen Evolution and Oxygen Reduction Reactions in Acidic Media Catalyzed by Pd₄S Decorated N/S Doped Carbon Derived from Pd Coordination Polymer

Hydrogen Evolution and Oxygen Reduction Reactions in Acidic Media Catalyzed by Pd₄S Decorated N/S Doped Carbon Derived from Pd Coordination Polymer