<i>De novo</i> synthesis of hybrid d–f block metal complex salts for electronic charge transport applications

Mahato, Shreya; Mondal, Amit; Das, Mainak; Joshi, Mayank; Ray, Partha Pratim; Roychoudhury, Angshuman; Reddy, C. Malla; Biswas, Bhaskar

doi:10.1039/d1dt02722k

Cited by 16 publications

(29 citation statements)

References 88 publications

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“…The complex salts 1 and 2 were synthesized by using a previously reported procedure . The corresponding metal salts were reacted with polypyridyl ligands with the subsequent addition of ceric ammonium nitrate in an aqueous acetic acid medium (60/40; v/v).…”

Section: Methodsmentioning

confidence: 99%

“…The complex salts 1 and 2 were synthesized by using a previously reported procedure. 45 The corresponding metal salts were reacted with polypyridyl ligands with the subsequent addition of ceric ammonium nitrate in an aqueous acetic acid medium (60/40; v/v). A NiNO 3 • 6H 2 O (0.1 mmol, 0.029 g) solution was added dropwise into 10 mL of a 1,10-phenanthroline solution (0.1 mmol, 0.040 g) and a 2,2′bipyridine (0.1 mmol, 0.032 g) solution separately under ambient conditions with slow stirring.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…■ RESULTS AND DISCUSSION Synthesis, Structural, and Morphological Characterization of the Complex Salts. The straightforward synthetic approach 45 through the facile stirring procedure enabled us to synthesize the [Ni(phen) 2 (NO 3 )] 2 [Ce(NO 3 ) 6 ] (1) and [Ni-…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…We found an interest in the electrical conductivity properties and stepped forward to investigate Ni(II)–Ce(IV) complex salts as smart electrocatalysts in hydrogen production. Fabrication studies for the Schottky device suggested that complex salt 2 , [Ni(bpy) 2 ][Ce(NO 3 ) 6 ] [Ce(H 2 O) 5 (NO 3 ) 2 ](NO 3 ), holds the highest charge transport ability with carrier mobility (μ) 8.22 × 10 –5 m 2 V –1 s –1 vs the complex salt 1 , [Ni(phen) 2 (NO 3 )] 2 [Ce(NO 3 ) 6 ], and previously reported structurally similar complex salts . To date, some expensive metal complexes have been incorporated to design smart materials with excellent functional properties. − Herein, we believe, our cost-effective synthetic hybrid salts may turn out to be a great functional resource with proper utility values.…”

Section: Introductionmentioning

confidence: 97%

“…37 We found an interest in the electrical conductivity , and previously reported structurally similar complex salts. 45 To date, some expensive metal complexes have been incorporated to design smart materials with excellent functional properties. 8−13 Herein, we believe, our cost-effective synthetic hybrid salts may turn out to be a great functional resource with proper utility values.…”

Section: ■ Introductionmentioning

confidence: 99%

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Supramolecular Framework-Driven Electrical Conductivities and Hydrogen Evolution Activities of Hybrid Nickel(II)–Cerium(IV) Complex Salts Cooperativity

Diyali

Das

et al. 2022

Crystal Growth & Design

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This work highlights the design, synthesis, structural characterization, electrical conductivities, and hydrogen evolution activities of a new pair of hybrid 3d(Ni)-4f(Ce) block metal complex salts, [Ni(phen)2(NO3)]2[Ce(NO3)6] (1) and [Ni(bpy)3][Ce(NO3)6][Ce(NO3)2(H2O)5]NO3 (2) containing phen and bpy ligands; [phen = 1,10-phenanthroline and bpy = 2,2′-bipyridine]. Crystal structural analysis divulges that complex salt 1 adopts two units of monocationic Ni(II) complex with one dianionic Ce(IV) complex unit while complex salt 2 exists in an association of one unit of dicationic Ni(II) complex with two complex units of Ce along with a counteranionic nitrate. The Ni(II) ions exist in distorted bicapped square pyramidal coordination geometry, while the Ni(II) center in 2 exists in an octahedral geometry. The cerium ion in 1 exists in dodecahedron geometry while the first and second Ce ions hold dodecahedral and tricapped trigonal prism coordination geometries, respectively. Supramolecular interactions reveal that predominant nonclassical forces like O···H, N···H, π···π, O···π, and O···O are interactive to shape highly ordered crystalline frameworks. Complex salt 2 exhibits a unique formation of the supramolecular cage-type framework by the cerium complex units, leading to the inclusion of Ni(II)-complex units into the supramolecular cages. The complex salts (1, 2) were employed to fabricate the Schottky devices to unveil the fate of the hybrid salts in charge transport applications. Carrier mobility (μ) for 1 and 2 were determined as 3.02 × 10–6 and 8.022 × 10–5 m2 V–1 s–1 with respective transit time(τ) of 2.60 × 10–7 and 9.67 × 10–9 s attributing the excellent candidature of complex salt 2 in transport properties. The hybrid salts were also found to be highly active electrocatalysts for proton reduction in 1 M aqueous KOH solution at room temperature. The overpotential values of 1 and 2 were determined to be 730 mV and 687 mV at a current density of 10 mA cm–2 with 0.081 s–1 and 0.225 s–1 as turnover frequencies. The supramolecular interactions–driven crystalline framework sheds light on the electrical conductivities and casting the hydrogen evolution activities for the newly designed hybrid d–f type complex salts.

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Section: Methodsmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 97%

Section: ■ Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Supramolecular Framework-Driven Electrical Conductivities and Hydrogen Evolution Activities of Hybrid Nickel(II)–Cerium(IV) Complex Salts Cooperativity

Diyali

Das

et al. 2022

Crystal Growth & Design

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Comparison of Electrical Conductivity and Schottky Behavior of 4‐[2‐(9‐anthryl)vinyl]pyridine Based Two 1D Coordination Polymers of Zn(II) and Cd(II)

Hossain,

Sk,

Das

et al. 2024

Eur J Inorg Chem

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With the increase in demand of electronic devices in the modern civilization, research in material science is being projected to grow in faster rate. In this facet, coordination polymer (CP) based electronic device is one of the promising candidates to the material researchers. Herein, two new Zn(II) and Cd(II) based one‐dimensional (1D) CPs, denoted as [Zn(4‐avp)2(5‐nip)]·(solvent)x (1) and [Cd(4‐avp)(5‐nip)(CH3OH)] (2) have been synthesized using relatively less explored highly conjugated polycyclic aromatic hydrocarbon (PAH) based monodentate ligand, 4‐[2‐(9‐anthryl)vinyl]pyridine (4‐avp) and bidentate linker 5‐nitroisophthalic acid (H25‐nip). In this instance, the CP 1 creates 1D chain polymer, while CP 2 is made up with 1D ladder polymer. It is interesting to note that both the CPs exhibit semiconducting nature and generate metal‐semiconductor (MS) junction Schottky barrier devices (SBDs). However, Cd‐based CP 2 shows higher charge transport as compared to Zn‐CP 1, which could be due to stronger π···π contacts as well as larger size of Cd metal in CP 2. The experimental results are well corroborated with theoretical density of states (DOS) calculations.

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Fabrication of Schottky Barrier Diodes Utilizing Schiff Base Compounds and Metal Complexes with Schiff Base Ligands

Dutta

Halder

2023

ChemistrySelect

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Fabrications of different kinds of diodes with various types of materials are the trends of modern research. In recent times organic materials and metal complexes containing organic ligands are chosen preferably for the fabrication of Schottky barrier diodes. Utilizations of Schiff‐base compounds and Schiff base containing metal complexes in the making of Schottky barrier diodes are immensely appreciated because the syntheses of Schiff‐base compounds are quite straightforward, less expensive and require less time. Large scale production of Schiff base materials is comparatively easier because their syntheses involve facile condensation reaction and their optical properties can be easily tuned by introducing simple substituent groups. Designing appropriate molecular structure plays pivotal role in the conducting properties of the materials. The molecular systems with exiting conducting properties can be utilized for the fabrication of such active electronic device. Sometimes, the specific structural arrangements enhance the charge flow upon illumination of light. These materials can be used in making photosensitive diode devices. In this context, this review, comprising of a collection of research articles regarding Schottky diode device based on Schiff bases and metal complexes with Schiff base ligands, may be helpful for the researchers of the relevant field.

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De novo synthesis of hybrid d–f block metal complex salts for electronic charge transport applications

Abstract: The advent of the d-d type of complex salts in designing smart functional materials of versatile utility inspired us to develop a novel type of M(II)-Ce(IV) complex salts [M(II) =...

Cited by 16 publications

References 88 publications

Supramolecular Framework-Driven Electrical Conductivities and Hydrogen Evolution Activities of Hybrid Nickel(II)–Cerium(IV) Complex Salts Cooperativity

Supramolecular Framework-Driven Electrical Conductivities and Hydrogen Evolution Activities of Hybrid Nickel(II)–Cerium(IV) Complex Salts Cooperativity

Comparison of Electrical Conductivity and Schottky Behavior of 4‐[2‐(9‐anthryl)vinyl]pyridine Based Two 1D Coordination Polymers of Zn(II) and Cd(II)

Fabrication of Schottky Barrier Diodes Utilizing Schiff Base Compounds and Metal Complexes with Schiff Base Ligands

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