Ligand-directed assembly and transformation of hybrid oxo-vanadates into 3d–3d oxo-vanado-cuprates: structural diversification and superior electrochemical performance in a prototype liquid-configured-device-grade supercapacitor

Oxo-vanadates, with their features of varied coordination and oxidation states, can form tunable structures, ranging from zero-dimensional ions or molecules to three-dimensional frameworks. Diphosphonate-functionalized oxovanadates, a recent inclusion into the family of oxovanadates, have formed diverse assemblies, particularly of mixed-valent oxovanadates. With pyridinyl-diphosphonate-functionalized oxovanadates, we have detected that the location of the nitrogen atom on the pyridine ring has strong structure- and symmetric-directing effects. To further explore the reactivity of the pyridinyl-dipshosphonate-functionalized oxo-vanadates, we reacted the mixed-valent oxo-vanadate polyanions [(V<sup>IV</sup>O<sub>2</sub>)(VV2O<sub>5</sub>)<sub>2</sub>{O<sub>3</sub>P-C(O)(CH<sub>2</sub>-<i>n</i>-C<sub>5</sub>NH<sub>4</sub>)-PO<sub>3</sub>}<sub>2</sub>]<sup>10-</sup> (<i>n</i> = 2 or 3) with copper(II) salt. This resulted in the formation of two novel 3d-3d mixed-metal hybrid oxo-vanado-cuprate polyanions: the cube-shaped [(Cu<sup>II</sup>)<sub>2</sub>(V<sup>IV</sup>O<sub>2</sub>)<sub>2</sub>(V<sup>V</sup>O<sub>2</sub>)<sub>4</sub>{O<sub>3</sub>P-C(O)(CH<sub>2</sub>-2-C<sub>5</sub>NH<sub>4</sub>)-PO<sub>3</sub>}<sub>4</sub>]<sup>12-</sup> (CuV-1) and the sinusoidal one-dimensional chain [{Cu<sup>II</sup>(H<sub>2</sub>O)<sub>2</sub>(CH<sub>3</sub>COO)}(V<sup>IV</sup>O<sub>2</sub>)(VV2O<sub>5</sub>)<sub>2</sub>{HO<sub>3</sub>P-C(O)(CH<sub>2</sub>-3-C<sub>5</sub>NH<sub>4</sub>)-PO<sub>3</sub>H}<sub>2</sub>]<sup>7-</sup> (CuV-2). These polyanions crystallized as (H<sub>3</sub>O)<sub>12</sub>[(Cu<sup>II</sup>)<sub>2</sub>(V<sup>V</sup>O<sub>2</sub>)<sub>4</sub>(V<sup>IV</sup>O<sub>2</sub>)<sub>2</sub>{O<sub>3</sub>P-C(O)(CH<sub>2</sub>-2-C<sub>5</sub>NH<sub>4</sub>)-PO<sub>3</sub>}<sub>4</sub>]·5.5H<sub>2</sub>O (CuV-1a) and (H<sub>3</sub>O)<sub>7</sub>[{Cu<sup>II</sup>(H<sub>2</sub>O)<sub>2</sub>(CH<sub>3</sub>COO)}(V<sup>IV</sup>O<sub>2</sub>)(VV2O<sub>5</sub>)<sub>2</sub>{HO<sub>3</sub>P-C(O)(CH<sub>2</sub>-3-C<sub>5</sub>NH<sub>4</sub>)-PO<sub>3</sub>H}<sub>2</sub>]·1.56H<sub>2</sub>O (CuV-2a), in the monoclinic space group of <i>C</i>2/<i>c</i> and orthorhombic space group of <i>Pnna</i>, respectively. The unique assembly of these mixed-metal polyanions is once again attributed to the strong structure-directing effects of the location of the nitrogen atom on the pyridinyl diphosphonate ligands, which resulted in isostructural oxo-vanadates capable of producing completely different assemblies. The oxidation states of the metal centres were established from bond valence sum (BVS) calculations and confirmed through multiple spectroscopic studies. Electrochemical energy-storage studies of the oxo-vanado-cuprate compounds revealed their enhanced redox activity and conductivity with respect to the parent oxo-vanadate compounds. Improvement was observed across all metrics, including the specific capacitance, energy density, power density, and cyclic stability. Hands-on implementation was performed using a fabricated liquid-type symmetric supercapacitor device to power LEDs and a small fan, making these compounds promising candidates for practical applications in high-performance supercapacitors with improved energy-storage efficiency.

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Journal
Dalton Transactions
Published
2025-01-01
DOI
https://doi.org/10.1039/d5dt01786f
Citations
2
Primary Topic
Polyoxometalates: Synthesis and Applications
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article
Field-Weighted Citation Impact
1.04
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article

Ligand-directed assembly and transformation of hybrid oxo-vanadates into 3d–3d oxo-vanado-cuprates: structural diversification and superior electrochemical performance in a prototype liquid-configured-device-grade supercapacitor

Abhishek Banerjee, Babasaheb R. Sankapal, Kartik Chandra Mondal, S. Rafi Ahamed et al.
2 citations
Dalton Transactions
Polyoxometalates: Synthesis and Applications
1.04
article

Ligand-directed assembly and transformation of hybrid oxo-vanadates into 3d–3d oxo-vanado-cuprates: structural diversification and superior electrochemical performance in a prototype liquid-configured-device-grade supercapacitor

Abhishek Banerjee, Babasaheb R. Sankapal, Kartik Chandra Mondal, S. Rafi Ahamed, Rajulal Sahu, Saurav Ghosh, Kalyankumar S. Morla
article en
2 citations

Abstract

Oxo-vanadates, with their features of varied coordination and oxidation states, can form tunable structures, ranging from zero-dimensional ions or molecules to three-dimensional frameworks. Diphosphonate-functionalized oxovanadates, a recent inclusion into the family of oxovanadates, have formed diverse assemblies, particularly of mixed-valent oxovanadates. With pyridinyl-diphosphonate-functionalized oxovanadates, we have detected that the location of the nitrogen atom on the pyridine ring has strong structure- and symmetric-directing effects. To further explore the reactivity of the pyridinyl-dipshosphonate-functionalized oxo-vanadates, we reacted the mixed-valent oxo-vanadate polyanions [(V<sup>IV</sup>O<sub>2</sub>)(VV2O<sub>5</sub>)<sub>2</sub>{O<sub>3</sub>P-C(O)(CH<sub>2</sub>-<i>n</i>-C<sub>5</sub>NH<sub>4</sub>)-PO<sub>3</sub>}<sub>2</sub>]<sup>10-</sup> (<i>n</i> = 2 or 3) with copper(II) salt. This resulted in the formation of two novel 3d-3d mixed-metal hybrid oxo-vanado-cuprate polyanions: the cube-shaped [(Cu<sup>II</sup>)<sub>2</sub>(V<sup>IV</sup>O<sub>2</sub>)<sub>2</sub>(V<sup>V</sup>O<sub>2</sub>)<sub>4</sub>{O<sub>3</sub>P-C(O)(CH<sub>2</sub>-2-C<sub>5</sub>NH<sub>4</sub>)-PO<sub>3</sub>}<sub>4</sub>]<sup>12-</sup> (CuV-1) and the sinusoidal one-dimensional chain [{Cu<sup>II</sup>(H<sub>2</sub>O)<sub>2</sub>(CH<sub>3</sub>COO)}(V<sup>IV</sup>O<sub>2</sub>)(VV2O<sub>5</sub>)<sub>2</sub>{HO<sub>3</sub>P-C(O)(CH<sub>2</sub>-3-C<sub>5</sub>NH<sub>4</sub>)-PO<sub>3</sub>H}<sub>2</sub>]<sup>7-</sup> (CuV-2). These polyanions crystallized as (H<sub>3</sub>O)<sub>12</sub>[(Cu<sup>II</sup>)<sub>2</sub>(V<sup>V</sup>O<sub>2</sub>)<sub>4</sub>(V<sup>IV</sup>O<sub>2</sub>)<sub>2</sub>{O<sub>3</sub>P-C(O)(CH<sub>2</sub>-2-C<sub>5</sub>NH<sub>4</sub>)-PO<sub>3</sub>}<sub>4</sub>]·5.5H<sub>2</sub>O (CuV-1a) and (H<sub>3</sub>O)<sub>7</sub>[{Cu<sup>II</sup>(H<sub>2</sub>O)<sub>2</sub>(CH<sub>3</sub>COO)}(V<sup>IV</sup>O<sub>2</sub>)(VV2O<sub>5</sub>)<sub>2</sub>{HO<sub>3</sub>P-C(O)(CH<sub>2</sub>-3-C<sub>5</sub>NH<sub>4</sub>)-PO<sub>3</sub>H}<sub>2</sub>]·1.56H<sub>2</sub>O (CuV-2a), in the monoclinic space group of <i>C</i>2/<i>c</i> and orthorhombic space group of <i>Pnna</i>, respectively. The unique assembly of these mixed-metal polyanions is once again attributed to the strong structure-directing effects of the location of the nitrogen atom on the pyridinyl diphosphonate ligands, which resulted in isostructural oxo-vanadates capable of producing completely different assemblies. The oxidation states of the metal centres were established from bond valence sum (BVS) calculations and confirmed through multiple spectroscopic studies. Electrochemical energy-storage studies of the oxo-vanado-cuprate compounds revealed their enhanced redox activity and conductivity with respect to the parent oxo-vanadate compounds. Improvement was observed across all metrics, including the specific capacitance, energy density, power density, and cyclic stability. Hands-on implementation was performed using a fabricated liquid-type symmetric supercapacitor device to power LEDs and a small fan, making these compounds promising candidates for practical applications in high-performance supercapacitors with improved energy-storage efficiency.

Dalton TransactionsVol. 54(46)
Visvesvaraya National Institute of Technology (IN), Indian Institute of Technology Madras (IN)
Openalex Percentile: Top 21%
Polyoxometalates: Synthesis and Applications
1.04
DOISourceOpenAlex
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