Unusual octahedral Hg(II) dithiocarbamate: Synthesis, spectral and structural studies on Hg(II) complexes with pyrrole based dithiocarbamates and their utility for the preparation of α- and β-HgS

Gurumoorthy, Govindasamy; Thirumaran, S.; Ciattini, Samuele

doi:10.1016/j.poly.2016.08.001

Cited by 21 publications

(9 citation statements)

References 31 publications

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“…In 2011, Ajibade and co-workers reported the first solvothermal decomposition, heating unsymmetrically substituted [Hg(S 2 CNRPh) 2 ] (R = Me, Et) in TOP/HDA at 120 °C for 1 h . Following this, the same group have reported similar solvothermal decomposition of a wide range of such complexes, ,,− including making poly(methyl methacrylate) (PMMA)/HgS composites. , Thirumaran and co-workers also described solvothermal decomposition of mercury bis-DTCs together with some pyridine and 2,2′-bipyridine adducts, normally through heating in a bi- or tridentate amine for 15 min. ,− Product morphologies vary depending upon the nature of the SSP. Generally mixtures of α-HgS and β-HgS result, the ratios of which depend upon both the SSP, solvent, and reaction conditions, but in some cases pure α-HgS is formed .…”

Section: Binary Sulfidesmentioning

confidence: 97%

“…Until recently, they have been relatively unexplored as QDs despite having optical properties with potential applications in solar energy conversion, optical amplification, and biological imaging . By far the most common DTC complexes of mercury are bis(DTCs) and [Hg(S 2 CNR 2 ) 2 ], which are easily prepared and adopt six different structural forms in the solid state, , while aryl complexes, [ArHg(S 2 CNR 2 )], are also relatively common …”

Section: Binary Sulfidesmentioning

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: Binary Sulfidesmentioning

confidence: 97%

Section: Binary Sulfidesmentioning

confidence: 99%

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

2021

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“…The extended coordination geometry is S 4 + S 2 , with the weakly associated sulphur atoms mutually trans. Supramolecular aggregation via intermolecular Hg … S secondary bonding interactions is also found in each of Hg[S2CN(n-Bu)CH2(1H-pyrrol-2-yl)] (161) [152] and Hg{S2CN[CH2(4-py)]CH2(1H-pyrrol-2-yl)} (162) [146]. In 161, relatively small differences in the Hg-S bond lengths, that is, 2.48 to 2.65 Å , are noted in the distorted tetrahedral geometry, with the widest angle being 138°.…”

Section: Mercury Dithiocarbamatesmentioning

confidence: 99%

“…The values of τ for each of the independent mercury atoms are equal at 0.57, consistent with highly distorted S5 coordination geometries. The last structure to be described, that is, [Hg{S2CN[(CH2)2Ph]CH2(1H-pyrrol-2-yl)}2]n (185) [152], conforms to motif V, being a linear coordination polymer, Figure 18b, as each dithiocarbamate ligand is tri-connective, chelating one mercury atom while simultaneously bridging another; the mercury atom lies on a 2-fold axis. …”

Section: Overview and Conclusionmentioning

confidence: 99%

Exploring the Topological Landscape Exhibited by Binary Zinc-triad 1,1-dithiolates

Tiekink

2018

Crystals

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Abstract:The crystal chemistry of the zinc-triad binary 1,1-dithiolates, that is, compounds of xanthate [ − S 2 COR], dithiophosphate [ − S 2 P(OR) 2 ], and dithiocarbamate [ − S 2 CNR 2 ] ligands, is reviewed. Owing to a wide range of coordination modes that can be adopted by 1,1-dithiolate anions, such as monodentate, chelating, µ 2 -bridging, µ 3 -bridging, etc., there exists a rich diversity in supramolecular assemblies for these compounds, including examples of zero-, one-, and two-dimensional architectures. While there are similarities in structural motifs across the series of 1,1-dithiolate ligands, specific architectures are sometimes found, depending on the metal centre and/or on the 1,1-dithiolate ligand. Further, an influence of steric bulk upon supramolecular aggregation is apparent. Thus, bulky R groups generally preclude the close approach of molecules in order to reduce steric hindrance and therefore, lead to lower dimensional aggregation patterns. The ligating ability of the 1,1-dithiolate ligands also proves crucial in determining the extent of supramolecular aggregation, in particular for dithiocarbamate species where the relatively greater chelating ability of this ligand reduces the Lewis acidity of the zinc-triad element, which thereby reduces its ability to significantly expand its coordination number. Often, the functionalisation of the organic substituents in the 1,1-dithiolate ligands, for example, by incorporating pyridyl groups, can lead to different supramolecular association patterns. Herein, the diverse assemblies of supramolecular architectures are classified and compared. In all, 27 structurally distinct motifs have been identified.

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“…Thus, metal dithiocarbamate complexes have been extensively studied in the area of crystal growth and design and as single source precursors for metal sulfide crystal synthesis. 1,4,7,9,[17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33] Of particular relevance to the current work, mercury (II) dithiocarbamate complexes produce a diverse range of molecular architectures and isomers; generating at least five distinct structural motifs in systems bearing two dithiocarbamate ligands. 1 The reaction of HgCl2 with diethyldithiocarbamate has been reported to produce three unique crystals (two polymorphs and an isomer) during crystal growth.…”

Section: Introductionmentioning

confidence: 99%

An Unusual Mercury(II) Diisopropyldithiocarbamate Coordination Polymer

Angeloski

Rawal

Bhadbhade

et al. 2019

Crystal Growth & Design

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A new polymeric mercury(II) di-isopropyldithiocarbamate complex was synthesized by the reaction of sodium di-isopropyldithiocarbamate with excess HgCl2 in water. The precise structure of the new compound was determined by single crystal X-ray diffraction. A similar reaction, using a stoichiometric excess of the ligand, yielded the known monomeric bis(di(isopropyl)dithiocarbamato)mercury(II) complex. The complexes could not be distinguished from each other by their solution phase NMR spectra nor their FTIR spectra. Solid state NMR spectroscopy ( 199 Hg and 13 C) provided unambiguous data and showed that the monomeric complex and polymeric complex do not interconvert in solution or during crystal growth.Thermogravimetric experiments revealed quite different thermal decomposition behaviour between the two compounds.

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Unusual octahedral Hg(II) dithiocarbamate: Synthesis, spectral and structural studies on Hg(II) complexes with pyrrole based dithiocarbamates and their utility for the preparation of α- and β-HgS

Cited by 21 publications

References 31 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

Exploring the Topological Landscape Exhibited by Binary Zinc-triad 1,1-dithiolates

An Unusual Mercury(II) Diisopropyldithiocarbamate Coordination Polymer

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