An atom efficient, single-source precursor route to plasmonic CuS nanocrystals

Mann, Patrick Bergstrom; McGregor, Iain; Bourke, Struan; Burkitt-Gray, Mary; Fairclough, Simon M.; Michelle, T.; Hogarth, Graeme; Thanou, Maya; Long, Nicholas J.; Green, Mark

doi:10.1039/c8na00325d

Cited by 17 publications

(15 citation statements)

References 22 publications

(31 reference statements)

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“…This is exemplified by a recent study of [Cu{S 2 CN(CH 2 CO 2 H) 2 } 2 ] which, unlike simple alkyl derivatives, has good water solubility, enabling self-capped copper-sulfide QDs to be generated in water. 36 A third type of DTC are those generated from primary amines. They are relatively easy to prepare, but the free ligands have a much smaller stability window than their disubstituted counterparts.…”

Section: Dithiocarbamates and Their Complexesmentioning

confidence: 99%

“…An increase of 15.1 °C was observed over 3 min, while the water control exhibited an increase of only 0.7 °C. 36 A second interesting recent development comes from Trindade and co-workers, who decomposed [Cu(S 2 CNEt 2 ) 2 ] and [Cu(S 2 CNBu 2 ) 2 ] at 240 °C in ionic liquids, obtaining digenite (Cu 9 S 5 ) nanocrystals as opposed to covellite, which was formed at the same temperature in OLA. 219 Ajibade and Botha have also reported that decomposition products of [Cu(S 2 CNBu 2 ) 2 ] in TOP/HDA are highly temperature dependent.…”

Section: Groupmentioning

confidence: 99%

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Dithiocarbamate Complexes as Single Source Precursors to Nanoscale Binary, Ternary and Quaternary Metal Sulfides

2021

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Nanodimensional metal sulfides are a developing class of low-cost materials with potential applications in areas as wide-ranging as energy storage, electrocatalysis, and imaging. An attractive synthetic strategy, which allows careful control over stoichiometry, is the single source precursor (SSP) approach in which well-defined molecular species containing preformed metal–sulfur bonds are heated to decomposition, either in the vapor or solution phase, resulting in facile loss of organics and formation of nanodimensional metal sulfides. By careful control of the precursor, the decomposition environment and addition of surfactants, this approach affords a range of nanocrystalline materials from a library of precursors. Dithiocarbamates (DTCs) are monoanionic chelating ligands that have been known for over a century and find applications in agriculture, medicine, and materials science. They are easily prepared from nontoxic secondary and primary amines and form stable complexes with all elements. Since pioneering work in the late 1980s, the use of DTC complexes as SSPs to a wide range of binary, ternary, and multinary sulfides has been extensively documented. This review maps these developments, from the formation of thin films, often comprised of embedded nanocrystals, to quantum dots coated with organic ligands or shelled by other metal sulfides that show high photoluminescence quantum yields, and a range of other nanomaterials in which both the phase and morphology of the nanocrystals can be engineered, allowing fine-tuning of technologically important physical properties, thus opening up a myriad of potential applications.

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Section: Dithiocarbamates and Their Complexesmentioning

confidence: 99%

Section: Groupmentioning

confidence: 99%

Dithiocarbamate Complexes as Single Source Precursors to Nanoscale Binary, Ternary and Quaternary Metal Sulfides

2021

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Section: Copper(ii) Bis(dithiocarbamate) Complexesmentioning

confidence: 99%

“…Many variants have been prepared, examples of which are shown in Figure 2. The addition of substituents to the end of alkyl chains (Figure 2a) allows tuning of the water solubility (e.g., X = OH) [16,30,31] and acid-base properties (e.g., X = CO2H or NEt2) [30,31]. Beer and co-workers have synthesised a series of macrocyclic complexes containing two (Figure 2b) or three Cu(II) bis(dithiocarbamate) centres [32][33][34], some of which serve as selective anion receptors [32,33].…”

Section: Copper(ii) Bis(dithiocarbamate) Complexesmentioning

confidence: 99%

“…In this way, thermolysis of [Cu{S 2 CN(CH 2 OH) 2 } 2 ] in water at 90 • C produces CuS nanospheres with a diameter of 8 ± 1 nm, showing a surface plasmon resonance at ca. 990 nm [31], and to demonstrate their potential therapeutic utility, their photothermal effect was measured using a 785 nm laser. An increase of 15.1 • C over 3 min was found, but this led only to a 2% loss of cervical cancer (HeLa) cells being observed after 24 h exposure in water.…”

Section: Binary Copper Sulfidesmentioning

confidence: 99%

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Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Hogarth

Onwudiwe

2021

Inorganics

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Copper dithiocarbamate complexes have been known for ca. 120 years and find relevance in biology and medicine, especially as anticancer agents and applications in materials science as a single-source precursor (SSPs) to nanoscale copper sulfides. Dithiocarbamates support Cu(I), Cu(II) and Cu(III) and show a rich and diverse coordination chemistry. Homoleptic [Cu(S2CNR2)2] are most common, being known for hundreds of substituents. All contain a Cu(II) centre, being either monomeric (distorted square planar) or dimeric (distorted trigonal bipyramidal) in the solid state, the latter being held together by intermolecular C···S interactions. Their d9 electronic configuration renders them paramagnetic and thus readily detected by electron paramagnetic resonance (EPR) spectroscopy. Reaction with a range of oxidants affords d8 Cu(III) complexes, [Cu(S2CNR2)2][X], in which copper remains in a square-planar geometry, but Cu–S bonds shorten by ca. 0.1 Å. These show a wide range of different structural motifs in the solid-state, varying with changes in anion and dithiocarbamate substituents. Cu(I) complexes, [Cu(S2CNR2)2]−, are (briefly) accessible in an electrochemical cell, and the only stable example is recently reported [Cu(S2CNH2)2][NH4]·H2O. Others readily lose a dithiocarbamate and the d10 centres can either be trapped with other coordinating ligands, especially phosphines, or form clusters with tetrahedral [Cu(μ3-S2CNR2)]4 being most common. Over the past decade, a wide range of Cu(I) dithiocarbamate clusters have been prepared and structurally characterised with nuclearities of 3–28, especially exciting being those with interstitial hydride and/or acetylide co-ligands. A range of mixed-valence Cu(I)–Cu(II) and Cu(II)–Cu(III) complexes are known, many of which show novel physical properties, and one Cu(I)–Cu(II)–Cu(III) species has been reported. Copper dithiocarbamates have been widely used as SSPs to nanoscale copper sulfides, allowing control over the phase, particle size and morphology of nanomaterials, and thus giving access to materials with tuneable physical properties. The identification of copper in a range of neurological diseases and the use of disulfiram as a drug for over 50 years makes understanding of the biological formation and action of [Cu(S2CNEt2)2] especially important. Furthermore, the finding that it and related Cu(II) dithiocarbamates are active anticancer agents has pushed them to the fore in studies of metal-based biomedicines.

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Coinage metal chalcogenides via single-source precursors

Arora

Oswal

Sharma

et al. 2022

Nanomaterials via Single-Source Precursors

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An atom efficient, single-source precursor route to plasmonic CuS nanocrystals

Abstract: The synthesis of colloidal semiconductor nanocrystals (NCs) from single-source precursors offers simplified manufacturing processes at the cost of reduced atom efficiency.

Cited by 17 publications

References 22 publications

Dithiocarbamate Complexes as Single Source Precursors to Nanoscale Binary, Ternary and Quaternary Metal Sulfides

Dithiocarbamate Complexes as Single Source Precursors to Nanoscale Binary, Ternary and Quaternary Metal Sulfides

Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Coinage metal chalcogenides via single-source precursors

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