Synthesis, solution dynamics and chemical vapour deposition of heteroleptic zinc complexes <i>via</i> ethyl and amide zinc thioureides

Bhide, Malavika A.; Mears, Kristian L.; Carmalt, Claire J.; Knapp, Caroline E.

doi:10.1039/d1sc01846a

Cited by 9 publications

(12 citation statements)

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“…Rather, we would suggest that ligand rearrangement is sufficiently fast at temperatures >258 K, to show an averaged signal for the { t Bu} groups in the 1 H NMR spectra. While we are unable to comment on the precise nature of the ligand rearrangement process, it seems reasonable to assume that a low-energy bond-breaking mechanism, with a calculated Δ G ‡ for the rearrangement process of Δ G ‡ = +46 kJ mol –1 , is most likely, as similar processes have been observed elsewhere …”

Section: Resultsmentioning

confidence: 80%

“…While we are unable to comment on the precise nature of the ligand rearrangement process, it seems reasonable to assume that a low-energy bond-breaking mechanism, with a calculated ΔG ‡ for the rearrangement process of ΔG ‡ = +46 kJ mol −1 , 17 is most likely, as similar processes have been observed elsewhere. 34 In the case of the adamantyl derivative, 4, meaningful interpretations of VT NMR data could not be obtained due to the overlapping resonances of the {NMe 2 } moieties and the various {CH} and {CH 2 } resonances associated with the adamantyl group.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Tin(II) Ureide Complexes: Synthesis, Structural Chemistry, and Evaluation as SnO Precursors

et al. 2021

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In an attempt to tailor precursors for application in the deposition of phase pure SnO, we have evaluated a series of tin (1–6) ureide complexes. The complexes were successfully synthesized by employing N,N′-trialkyl-functionalized ureide ligands, in which features such as stability, volatility, and decomposition could be modified with variation of the substituents on the ureide ligand in an attempt to find the complex with the ideal electronic, steric, or coordinative properties, which determine the fate of the final products. The tin(II) ureide complexes 1-6 were synthesized by direct reaction [Sn{NMe2}2] with aryl and alkyl isocyanates in a 1:2 molar ratio. All the complexes were characterized by NMR spectroscopy as well as elemental analysis and, where applicable, thermogravimetric (TG) analysis. The single-crystal X-ray diffraction studies of 2, 3, 4, and 6 revealed that the complexes crystallize in the monoclinic space group P2(1)/n (2 and 4) or in the triclinic space group P-1 (3 and 6) as monomers. Reaction with phenyl isocyanate results in the formation of the bimetallic species 5, which crystallizes in the triclinic space group P-1, a consequence of incomplete insertion into the Sn-NMe2 bonds, versus mesityl isocyanate, which produces a monomeric double insertion product, 6, under the same conditions, indicating a difference in reactivity between phenyl isocyanate and mesityl isocyanate with respect to insertion into Sn-NMe2 bonds. The metal centers in these complexes are all four-coordinate, displaying either distorted trigonal bipyramidal or trigonal bipyramidal geometries. The steric influence of the imido-ligand substituent has a clear effect on the coordination mode of the ureide ligands, with complexes 2 and 6, which contain the cyclohexyl and mesityl ligands, displaying κ2-O,N coordination modes, whereas κ2-N,N′ coordination modes are observed for the sterically bulkier tert-butyl and adamantyl derivatives, 3 and 4. The thermogravimetric analysis of the complexes 3 and 4 exhibited excellent physicochemical properties with clean single-step curves and low residual masses in their TG analyses suggesting their potential utility of these systems as MOCVD and ALD precursors.

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Section: Resultsmentioning

confidence: 80%

Section: ■ Results and Discussionmentioning

confidence: 99%

Tin(II) Ureide Complexes: Synthesis, Structural Chemistry, and Evaluation as SnO Precursors

et al. 2021

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“…[24] A chemical explanation to this lowering effect upon coordination with alkanolamines remains unclear, highlighting the urgent need to ascertain the link between molecular structure and precursor properties [26] to make more informed decisions about ligand choice. [27][28][29] There are few literature reports that attempt to establish this link [30] though Paquet et al [31,32] have recently reported the isolation of a range of MOD complexes synthesized by the reaction of copper(II) formate with various pyridines and primary and secondary amines. This study suggested a link between increased H-bonding between the formate counter ion and the NH group of the ligand (confirmed by single crystal X-ray diffraction (SCXRD)) and rising decomposition temperatures from TGA.…”

Section: Introductionmentioning

confidence: 99%

“…There are few literature reports that attempt to establish this link [ 30 ] though Paquet et al. [ 31,32 ] have recently reported the isolation of a range of MOD complexes synthesized by the reaction of copper(II) formate with various pyridines and primary and secondary amines.…”

Section: Introductionmentioning

confidence: 99%

Unraveling the Steric Link to Copper Precursor Decomposition: A Multi‐Faceted Study for the Printing of Flexible Electronics

et al. 2023

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The field of printed electronics strives for lower processing temperatures to move toward flexible substrates that have vast potential: from wearable medical devices to animal tagging. Typically, ink formulations are optimized using mass screening and elimination of failures; as such, there are no comprehensive studies on the fundamental chemistry at play. Herein, findings which describe the steric link to decomposition profile: combining density functional theory, crystallography, thermal decomposition, mass spectrometry, and inkjet printing, are reported. Through the reaction of copper(II) formate with excess alkanolamines of varying steric bulk, tris-co-ordinated copper precursor ions: "[CuL 3 ]," each with a formate counter-ion (1-3) are isolated and their thermal decomposition mass spectrometry profiles are collected to assess their suitability for use in inks (I 1-3 ). Spin coating and inkjet printing of I 1,2 provides an easily up-scalable method toward the deposition of highly conductive copper device interconnects (𝝆 = 4.7-5.3 × 10 −7 𝛀 m; ≈30% bulk) onto paper and polyimide substrates and forms functioning circuits that can power light-emitting diodes. The connection among ligand bulk, coordination number, and improved decomposition profile supports fundamental understanding which will direct future design.

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“…Other desired properties of an MOD ink include clean decomposition to target material without residual contaminants, 14 good solubility and long shelf life. 15 Additional pre-requisites for an MOD ink are highlighted in our recent review.…”

Section: Introductionmentioning

confidence: 99%

Deposition of metallic silver from versatile amidinate precursors for use in functional materials

Mrig

Jennings

Bhide

et al. 2022

Journal of Chemical Research

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Silver (Ag) amidinate metal organic decomposition precursors of the type: [Ag2((ArN)2C(H))2] (Ar = 2,6-dimethylphenyl (1), 2,6-diethylphenyl (2) and 2,6-diisopropylphenyl (3)) have been used for the first time in the deposition of Ag films on glass with multiple functionalities with potential application in optical/biological sensors or for use in electronic circuitry. Precursors 1–3 were isolated from the reaction of silver acetate with the appropriate ligand in a 1:2 stoichiometry and were characterized by 1H and 13C{1H} NMR, thermal gravimetric analysis and single crystal X-ray diffraction for 2. Single-layer depositions at 200 °C on glass substrates via spin coating produced transparent (>90% transmittance) coatings, with well-defined Ag nanoparticles. Multi-layer depositions at 200 °C on glass had a metallic lustre and were found to be conductive ( ρ = 0.916–1.83 × 10−6 Ωm). All films were strongly adhered and displayed excellent coverage of the substrate. Ag films deposited from 1 to 3 were analysed by grazing incidence X-ray diffraction, X-ray photoelectron spectroscopy, energy-dispersive X-ray analysis and scanning electron microscopy, with optical properties determined by UV-Vis spectroscopy.

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Synthesis, solution dynamics and chemical vapour deposition of heteroleptic zinc complexes via ethyl and amide zinc thioureides

Abstract: Ethyl and amide zinc thioureides [L1ZnEt]2 (1), [L1ZnEt]2 (2) and [L1Zn(N(SiMe3)2)]2 (3) have been synthesised from the equimolar reaction of thiourea ligands (HL1 = iPrN(H)CSNMe2 and HL1 = PhN(H)CSNMe2) with diethyl zinc and zinc...

Cited by 9 publications

References 43 publications

Tin(II) Ureide Complexes: Synthesis, Structural Chemistry, and Evaluation as SnO Precursors

Tin(II) Ureide Complexes: Synthesis, Structural Chemistry, and Evaluation as SnO Precursors

Unraveling the Steric Link to Copper Precursor Decomposition: A Multi‐Faceted Study for the Printing of Flexible Electronics

Deposition of metallic silver from versatile amidinate precursors for use in functional materials

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Synthesis, solution dynamics and chemical vapour deposition of heteroleptic zinc complexes via ethyl and amide zinc thioureides

Abstract: Ethyl and amide zinc thioureides [L1ZnEt]2 (1), [L1*ZnEt]2 (2) and [L1Zn(N(SiMe3)2)]2 (3) have been synthesised from the equimolar reaction of thiourea ligands (HL1 = iPrN(H)CSNMe2 and HL1* = PhN(H)CSNMe2) with diethyl zinc and zinc...

Cited by 9 publications

References 43 publications

Tin(II) Ureide Complexes: Synthesis, Structural Chemistry, and Evaluation as SnO Precursors

Tin(II) Ureide Complexes: Synthesis, Structural Chemistry, and Evaluation as SnO Precursors

Unraveling the Steric Link to Copper Precursor Decomposition: A Multi‐Faceted Study for the Printing of Flexible Electronics

Deposition of metallic silver from versatile amidinate precursors for use in functional materials

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Product

Resources

About

Abstract: Ethyl and amide zinc thioureides [L1ZnEt]2 (1), [L1ZnEt]2 (2) and [L1Zn(N(SiMe3)2)]2 (3) have been synthesised from the equimolar reaction of thiourea ligands (HL1 = iPrN(H)CSNMe2 and HL1 = PhN(H)CSNMe2) with diethyl zinc and zinc...