Ferrocene decorated homoleptic silver(I) clusters: Synthesis, structure, and their electrochemical behaviour

Khirid, Samreet; Jangid, Dilip Kumar; Biswas, Rathindranath; Meena, Sangeeta; Sahoo, Subash Chandra; Verma, Ved Prakash; Nandi, Chandan; Haldar, Krishna Kanta; Dhayal, Rajendra S.

doi:10.1016/j.jorganchem.2021.121923

Cited by 6 publications

(6 citation statements)

References 49 publications

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“…The solid-state structure of 1 unfolded as shown in Figure a and was found analogous to that of [Ag 4 {S 2 PFc(O i Pr)} 4 ], ( 5 ) . The pale-yellow cubic-shaped crystals were grown by slow diffusion of hexane in a chloroform solution of 1 .…”

Section: Resultssupporting

confidence: 70%

“…The square-shaped suitable single crystals of 2 with dark orange color were obtained by slow diffusion of diethyl ether into CHCl 3 . Unlike cluster 1 ( P 4/ n ), cluster 2 crystallizes in monoclinic space group C 2/ c , with eight molecules in the unit cell, which is similar to the reported cluster 5 ( C 2/ c ) . The solid-state structure of 2 was depicted in Figure , which clearly reveals the isostructural frame of all elements as found in 1 .…”

Section: Resultsmentioning

confidence: 86%

“…Unlike cluster 1 (P4/n), cluster 2 crystallizes in monoclinic space group C2/c, with eight molecules in the unit cell, which is similar to the reported cluster 5 (C2/c). 42 The solid-state structure of 2 was depicted in Figure 4, which clearly reveals the isostructural frame of all elements as found in 1. Additionally, these structures also exclude the possibility of existence of any counteranion, which is consistent with the 31 P NMR result.…”

Section: ■ Introductionmentioning

confidence: 89%

“…The solid-state structure of 1 unfolded as shown in Figure 3a and was found analogous to that of [Ag 4 {S 2 PFc(O i Pr)} 4 ], (5). 42 The paleyellow cubic-shaped crystals were grown by slow diffusion of hexane in a chloroform solution of 1. Structure 1 was solved in the tetragonal space group P4/n, with CHCl 3 solvent residue inside the unit cell.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The molecular structures of 1 , 2 , and 3 were established by single-crystal X-ray diffraction (SC-XRD). All the molecules were explored in electrocatalytic water splitting for a hydrogen evolution reaction, where (R = i Pr, 5 ) was also comprised for consistency and comparison. Successively, these clusters differ either by incorporation of −CH 2 – or branching of a carbon chain within an alkoxy moiety of the Fc-dtop ligand, and they raised a systematic steric hindrance around the metallic Ag 4 core in appropriate way, which reflects the HER activity.…”

Section: Introductionmentioning

confidence: 99%

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Dithiophosphonate Anchored Heterometallic (Ag(I)/Fe(II)) Molecular Catalysts for Electrochemical Hydrogen Evolution Reaction

et al. 2022

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The dichalcogenide ligated molecules in catalysis to produce molecular hydrogen through electroreduction of water are rarely explored. Here, a series of heterometallic [Ag 4 (S 2 PFc(OR) 4 ] [where Fc = Fe(η 5 -C 5 H 4 )(η 5 -C 5 H 5 ), R = Me, 1; Et, 2; n Pr, 3; iso Amyl, 4] clusters were synthesized and characterized by IR, absorption spectroscopy, NMR ( 1 H, 31 P), and electrospray ionization mass spectrometry. The molecular structures of 1, 2, and 3 clusters were established by single-crystal X-ray crystallographic analysis. The structural elucidation shows that each triangular face of a tetrahedral silver(I) core is capped by a ferrocenyl dithiophosphonate ligand in a trimetallic triconnective (η 3 ; μ 2 , μ 1 ) pattern. A comparative electrocatalytic hydrogen evolution reaction of 1−5 (R = i Pr, 5) was studied in order to demonstrate the potential of these clusters in water splitting activity. The experimental results reveal that catalytic performance decreases with increases in the length of the carbon chain and branching within the alkoxy (-OR) group of these clusters. Catalytic durability was found effective even after 8 h of a chronoamperometric stability test along with 1500 cycles of linear sweep voltammetry performance, and only 15 mV overpotential was increased at 5 mA/cm 2 current density for cluster 1. A catalytic mechanism was proposed by applying density functional theory (DFT) on clusters 1 and 2 as a representative. Here, a μ 1 coordinated S-site between Ag 4 core and ligand was found a reaction center. The experimental results are also in good accordance with the DFT analysis.

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Section: Resultssupporting

confidence: 70%

Section: Resultsmentioning

confidence: 86%

Section: ■ Introductionmentioning

confidence: 89%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Dithiophosphonate Anchored Heterometallic (Ag(I)/Fe(II)) Molecular Catalysts for Electrochemical Hydrogen Evolution Reaction

et al. 2022

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Ferrocenyl Dithiophosphonate Ag(I) Complexes: Synthesis, Structures, Luminescence, and Electrocatalytic Water Splitting Tuned by Nuclearity and Ligands

Kumar Jangid,

Dastider,

Mandal

et al. 2024

Chemistry A European J

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The heterometallic [Ag(I)/Fe(II)] molecular electrocatalysts for hydrogen production were introduced here to recognize the mutual role of metallic nuclearity and ligand engineering. A series of ferrocenyl dithiophosphonate stabilized mononuclear [Ag(PPh3)2{S2PFc(OR)}] {where R=Me (1), Et (2), nPr (3), iPr (4), iAmyl (5); Fc=Fe (ɳ5‐C5H4) (ɳ5‐C5H5)} and dinuclear [Ag(PPh3){S2PFc(OR}]2 {where R=Et (2 a), and nPr (3 a)} complexes were synthesized and characterized by SCXRD, NMR (31P and 1H), ESI‐MS, UV‐Vis, and FT‐IR spectroscopy. The comparative electrocatalytic HER behavior of 1–5 and 2 a–3 a showed effective current density of 1 mA/cm2 with overpotentials ranging from 772 to 991 mV, demonstrating the influence of extended and branched carbon chains in dithiophosphonates and metallic (mono‐/di−) nuclearity, which correlates with documented tetra‐nuclear [Ag4(S2PFc(OnPr)4], 6. DFT study suggests the coordinated (μ1‐S) site of ligands is the reactivity center and the adsorption energy of intermediate [H*‐SM] varies with the engineering of ligand and nuclearity. A catalytic mechanism using mononuclear (1) and di‐nuclear (2 a) was proposed with the assistance of DFT. Each complex, being the first example of Ag(I) dithiophosphonates, exhibits intense photoluminescence with high quantum yields ranging from 33 % to 67 %. These results link the lower nuclearity structures to their physical and catalytic properties.

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Antimicrobial and Gas Adsorption Properties of Electrospun Ferrocene-Polyurethane-Based Nanofibers Containing Silver Nitrate

Yılmaz

2022

Arab J Sci Eng

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Ferrocene decorated homoleptic silver(I) clusters: Synthesis, structure, and their electrochemical behaviour

Cited by 6 publications

References 49 publications

Dithiophosphonate Anchored Heterometallic (Ag(I)/Fe(II)) Molecular Catalysts for Electrochemical Hydrogen Evolution Reaction

Dithiophosphonate Anchored Heterometallic (Ag(I)/Fe(II)) Molecular Catalysts for Electrochemical Hydrogen Evolution Reaction

Ferrocenyl Dithiophosphonate Ag(I) Complexes: Synthesis, Structures, Luminescence, and Electrocatalytic Water Splitting Tuned by Nuclearity and Ligands

Antimicrobial and Gas Adsorption Properties of Electrospun Ferrocene-Polyurethane-Based Nanofibers Containing Silver Nitrate

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