Mono and trivalent thallium–sulfur interactions and their influence on the formation of nano thallium sulphide: single crystal X-ray structural and spectral studies on thallium(<scp>i</scp>)/(<scp>iii</scp>)–cyclohexylpiperazine dithiocarbamates

Ramalingam, K.; Rizzoli, Corrado; Sivagurunathan, G.S.

doi:10.1039/c5nj02980e

Cited by 16 publications

(6 citation statements)

References 61 publications

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“…10 nm by HRTEM . Somewhat contradictory to this finding, Ramalingam and co-workers have recently reported that heating the cyclohexylpiperazine DTC complex, [Tl(S 2 CNC 5 H 9 –Cy)] 2 , in chloroform with added DTA at 60 °C for 45 min affords Tl 4 S 3 . They also report that the analogous Tl(III) complex also gives Tl 4 S 3 under the same conditions, although its formation is slower than from the Tl(I) precursor, and this appears to be a general difference …”

Section: Binary Sulfidesmentioning

confidence: 93%

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: 93%

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

2021

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Section: Synthesismentioning

confidence: 99%

“…The molecular refined structure is presented as well as the peculiar Tl 2 S 4 ring in [Tl(chpzdtc)] 2 which is missing in [Tl(chpzdtc)] 3 ·C 6 H 6 , making the first compound more prone to the decomposition to nano‐Tl 4 S 3 during the solvothermal step. [ 214 ] The structures of the two compounds showed a dimeric, 6‐membered ring (Tl 2 S 4 ) as core of the structure for the Tl(chpzdtc) 2 and a distorted, octahedral, monomeric centers for Tl(chpzdtc) 3 . The difference in structures has shown that only the first compound was able to form Tl 4 S 3 , thanks to the strongly directional lozenge pattern that is visible in the crystal structure.…”

Section: Thallium Chalcogenidesmentioning

confidence: 99%

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A New, Thorough Look on Unusual and Neglected Group III‐VI Compounds Toward Novel Perusals

Guzzetta

Jellett

Azadmanjiri

et al. 2023

Small

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been permitted. [4][5][6][7] Although, the employment of 2D nanosheets, especially in biomedicine, is still in its primordial state and has permitted to the realization of novel advancements in such applications. [8][9][10] It needs to be highlighted that some of these compounds present mild cytotoxicity and dose-dependent induced metabolic disadvantages. [11,12] Albeit direct use in the body is not yet advisable, it is possible to indirectly employ these compounds in the creation of wearable devices for tracking vital parameters. [13] Research on such topics, both from fundamental and applied studies has led to an exponential increase in the number of publications during the last 10 years (Figure 1c). [14] One of the pivotal characteristics of 2D nanostructures is their high specific area-to-thickness ratio, which can be easily modulated through delamination processes. [15] Ultimately, the smallest crystals that can be created are mono-or bi-atomic layers. To understand how the nanocrystals form from bulk, it is important to comprehend the main characteristic features of the macrocrystals. A layered crystal lattice is presented in Figure 2. These crystals are governed by strong, covalent (or ionic) in-plane bonds, which are often arranged into hexagonal honeycombs. These individual sheets are linked together by inter-plane (inter-layer), and weak van der Waals (vdW) forces. The bond energies between the in-plane atoms, are the major contribution on the total energy of the lattice, leaving weak inter-plane interactions with relatively large distances (i.e., about few hundred picometers in graphene). These large inter-planar spaces are suitable attack points for size reduction, [16][17][18] which requires an external energy input from a providing source in order to delaminate single-layer crystals.The in-plane honeycomb structure is responsible for electrical transport and associated phenomena. For instance, the great mobility of p-electrons and their delocalization on the surface allows excellent transport in graphene. [23,24] However, in some other electro-and photoactivated semiconductors based on 2D materials, the electrical transport on the surface is responsible for the hole-electron confinement. [25] It can also produce poor electrical conduction by 2D materials such as hexagonal boron nitride (hBN) and so making them electrical insulators (see Figure 1a). [26] These differences in the layersThe attention on group III-VI compounds in the last decades has been centered on the optoelectronic properties of indium and gallium chalcogenides. These outstanding properties are leading to novel advancements in terms of fundamental and applied science. One of the advantages of these compounds is to present laminated structures, which can be exfoliated down to monolayers. Despite the large knowledge gathered toward indium and gallium chalcogenides, the family of the group III-VI compounds embraces several other noncommon compounds formed by the other group III elements. These compounds present various crystal lattices...

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“…Additionally, the reduction potential for Tl 3+ is dependent on both the pH and the complexing ligands . While structures containing trivalent thallium are knownsuch as some polyoxometalates (POMs), , superconductors, perovskites, , and a few standalone structures − they are overshadowed by their monovalent counterparts. The chemistry of monovalent thallium most closely resembles that of the later alkaline metals and silver due to its similar ionic radius (1.54 vs 1.44, 1.58, and 1.27 Å for K + , Rb + , and Ag + , respectively) .…”

Section: Introductionmentioning

confidence: 99%

Lanthanide Squarate Complexes Containing Mono- and Trivalent Thallium

Ball

Polinski

2023

Inorg. Chem.

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The synthesis and structural characterization of 16 new thallium lanthanide squarate complexes and 1 new cerium squarate oxalate complex are presented. These new complexes�Tl 4)�all contain the squarate ligand bound to the trivalent lanthanides with varying coordination modes and denticities. Of the four new groups of complexes prepared in this work, two groupings contain monovalent thallium and trivalent lanthanides, the most common oxidation states for these metals. One complex (3), however, contains trivalent thallium, which is an unusual and challenging oxidation state to stabilize. The Tl 3+ cation is formed from in situ oxidation by way of tetravalent cerium (Ce 4+ /Ce 3+ , E°= 1.72 V; Tl 3+ /Tl + = 1.252 V), leading to the formation of a Tl 3+ -Ce 3+ -squarate complex. Additionally, one complex ( 4) is unique in this work in that it contains both the squarate and oxalate ligands, the latter of which was formed in situ from squarate. Single-crystal X-ray diffraction analysis reveals that 1 and 2 have a 2D structure constructed from either LnO 4 (H 2 O) 5 monocapped square antiprismatic (CN = 9) metal centers (for 1) or LnO 4 (H 2 O) 4 square antiprismatic (CN = 8) metal centers (for 2), 3 is a 1D chain structure constructed from CeO 3 (H 2 O) 6 monocapped square antiprismatic (CN = 9) cerium centers, and 4 is a 3D framework structure constructed from CeO 5 (H 2 O) 4 monocapped square antiprismatic (CN = 9) cerium centers. 2 and 4 display rare coordination modes for the squarate ligand. Herein, the synthesis, characterization, and structural descriptions of these new complexes are presented.

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Mono and trivalent thallium–sulfur interactions and their influence on the formation of nano thallium sulphide: single crystal X-ray structural and spectral studies on thallium(i)/(iii)–cyclohexylpiperazine dithiocarbamates

Abstract: Tl–S bond distances in (1) are longer than in (2) and hence the greater ease of solvothermal decomposition of (1) to nano Tl4S3 than (2).

Cited by 16 publications

References 61 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

A New, Thorough Look on Unusual and Neglected Group III‐VI Compounds Toward Novel Perusals

Lanthanide Squarate Complexes Containing Mono- and Trivalent Thallium

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