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Journal Article•DOI•

Group 12 dithiocarbamate complexes: Synthesis, characterization, and X-ray crystal structures of Zn(II) and Hg(II) complexes and their use as precursors for metal sulfide nanoparticles

Peter A. Ajibade1, Johannes Z. Mbese1, Bernard Omondi2•
University of Fort Hare1, University of KwaZulu-Natal2
01 Feb 2017-Inorganic and Nano-Metal Chemistry (Taylor & Francis)-Vol. 47, Iss: 2, pp 202-212
TL;DR: In this paper, Zn(II, Cd(II), and Hg(II) dithiocarbamate complexes were synthesized and characterized by elemental analysis, thermogravimetric analysis, UV-Vis, FTIR, and 1H- and 13C-NMR spectroscopy.
Abstract: Zn(II), Cd(II), and Hg(II) dithiocarbamate complexes were synthesize and characterized by elemental analysis, thermogravimetric analysis, UV-Vis, FTIR, and 1H- and 13C-NMR spectroscopy. Single-crystal X-ray crystallography revealed that the Zn complex has a centrosymmetric dimeric structure while the Hg complex crystallizes with two monomeric molecules of the mercury complex and two molecules of toluene solvent in the asymmetric unit. The compounds were used as single molecule precursors to synthesize HDA capped metal sulfides nanoparticles with average crystallite size ranging from 7 to 22 nm. The optical properties of the nanoparticles showed evidence of quantum confinement.
Citations
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Journal Article•DOI•
Metal complexes of alkyl-aryl dithiocarbamates: Structural studies, anticancer potentials and applications as precursors for semiconductor nanocrystals

[...]

Fartisincha P. Andrew1, Peter A. Ajibade1•
University of KwaZulu-Natal1
05 Mar 2018-Journal of Molecular Structure
TL;DR: In this article, the synthesis, structural studies, anticancer potency and the use of alkyl-phenyl dithiocarbamate complexes as precursors for the preparation of semiconductor nanocrystals are reviewed.

47 citations

Journal Article•DOI•
Synthesis, characterization and anticancer studies of bis(1-phenylpiperazine dithiocarbamato) Cu(II), Zn(II) and Pt(II) complexes: Crystal structures of 1-phenylpiperazine dithiocarbamato-S,S′ zinc(II) and Pt(II)

[...]

Fartisincha P. Andrew1, Peter A. Ajibade1•
University of KwaZulu-Natal1
15 Oct 2018-Journal of Molecular Structure
TL;DR: In this paper, single crystal X-ray structures of the Zn(II), Pt(II) and Zn2(μ-L)2(L) 2(L 2 ) complexes are reported.

41 citations

Journal Article•DOI•
Exploring the Topological Landscape Exhibited by Binary Zinc-triad 1,1-dithiolates

[...]

Edward R. T. Tiekink
14 Jul 2018
TL;DR: The crystal chemistry of the zinc-triad binary 1, 1,1-dithiolates, that is, compounds of xanthate [−S2COR], dithiophosphate [ −S2P(OR)2], and dithIocarbamate [−CNR2] ligands, is reviewed in this article.
Abstract: The crystal chemistry of the zinc-triad binary 1,1-dithiolates, that is, compounds of xanthate [−S2COR], dithiophosphate [−S2P(OR)2], and dithiocarbamate [−S2CNR2] ligands, is reviewed. Owing to a wide range of coordination modes that can be adopted by 1,1-dithiolate anions, such as monodentate, chelating, μ2-bridging, μ3-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.

40 citations

Cites background from "Group 12 dithiocarbamate complexes:..."

  • ...142 i-Pr/i-Pr S4 M monomer [139] 143 Cy/Cy S4 M monomer [140] 144 Benzyl/Benzyl S4 M monomer [141] 145 R + R’ = (CH2)4 S4 M monomer [142] 146 i-Bu/i-Bu S4 K monomer [143] 147 R + R’ = (CH2)4NCH2C(H)=C(H)Ph S4 M monomer [144] 148 N(RR’) = R1 1 S4 M monomer [145] 149 2 Et/Ph S4 M monomer [101] 150 i-Pr/Cy S4 M monomer [143] 151 3 Me/Ph; n-Bu/Ph S4 M monomer [105] 152 Benzyl/CH2(1-Me-1H-pyrrol-2-yl) S4 M monomer [146] 153 Benzyl/CH2(ferrocenyl) S4 M monomer [147] 154 CH2(3-py)/CH2(1-Me-1H-pyrrol-2-yl) S4 M monomer [39] 155 CH2CH2OH/CH2(ferrocenyl) S4 M monomer [70] 156 Me/Me S4 X monomer [148] 157 Et/Et S4 X monomer [149] 158 Benzyl/CH2(3-py) S4 X monomer [72] 159 Benzyl/CH2(4-py) S4 X monomer [150] 160 CH2CH2OH/CH2CH2OH S4 X monomer [151] 161 n-Bu/CH2(1H-pyrrol-2-yl) S4 Y monomer [152] 162 CH2(4-py)/CH2(1H-pyrrol-2-yl) S4 Z monomer [146] 163 Et/Et S4 + 1 O dimer [149,153] 164 i-Pr/i-Pr S4 + 1 O dimer [154] 165 n-Bu/n-Bu S4 + 1 N dimer [143] 166 R + R’ = (CH2)4 S4 + 1 O dimer [155] 167 R + R’ = (CH2)5Me S4 + 1 O dimer [156] 168 R + R’ = (CH2)6 S4 + 1 O dimer [157] 169 CH2(2-furyl)/CH2(2-furyl) S4 + 1 O dimer [158] 170 Me/Ph S4 + 1 O dimer [159] 171 Me/(CH2)2Ph S4 + 1 O dimer [160] 172 Et/Cy S4 + 1 O dimer [143] 173 Et/Ph S4 + 1 O dimer [161] 174 i-Pr/CH2CH2OH S4 + 1 O dimer [162] 175 Benzyl/CH2(2-furyl) S4 + 1 O dimer [158] 176 (CH2)2Ph/CH2(2-furyl) S4 + 1 O dimer [163] 177 (CH2)2Ph/CH2CH2(thiophen-2-yl) S4 + 1 O dimer [163] 178 CH2(3-py)/CH2(ferrocenyl) S4 + 1 O dimer [109] 179 3 CH2(3-py)/CH2(1-naphthyl) NS4 Q dimer [39] 180 4 NRR’ = R2 5 2 × S5 + S6 S trimer [145] 181 Me/CH2(4-py) NS4 Z polymer [72] 182 CH2(3-py)/CH2(1,3-benzodioxo-5-yl) NS4 P polymer [72] 183 CH2(4-py)/CH2(2-furyl) N2S4 R layer [72] 184 (CH2)2Ph/CH2(3-py) NS5 AA polymer [72] 185 (CH2)2Ph/CH143(1H-pyrrol-2-yl) S6 V polymer [152] 1 R1 is 3,4-dihydroquinoline-1(2H); 2 tolyl hemi-solvate; 3 mono-ethanol solvate; 4 mono-pyridine solvate; 5 R2 is 1,2,3,4-tetrahydroquinoline....

    [...]

  • ...81 Et/n-Bu S4 + 1 O dimer [100] 82 Et/Cy S4 + 1 O dimer [25] 83 3 Et/Ph S4 + 1 O dimer [101] 84 5 Et/Ph S4 + 1 O dimer [102] 85 Et/CH2CH2OH S4 + 1 O dimer [83] 86 n-Pr/i-Pr S4 + 1 O dimer [103] 87 10 i-Pr/CH2CH2OH S4 + 1 O dimer [96] 88 c-Pr/CH2C6H4-4-OMe S4 + 1 O dimer [104] 89 n-Bu/Ph S4 + 1 O dimer [105] 90 Benzyl/(CH2)13Me S4 + 1 O dimer [106] 91 9 Benzyl/R2 9 S4 + 1 O dimer [74] 92 CH2(2-furyl)/CH2C6H4-4-Cl S4 + 1 O dimer [75] 93 CH2(2-furyl)/R(2) 9 S4 + 1 O dimer [74] 94 CH2C6H4-4-OMe/(CH2)2N(CH2CH2)2O S4 + 1 O dimer [74] 95 i-Bu/i-Bu S4 M monomer [107] S4 + 1 O 96 R + R’ = (CH2)4NMe NS4 P polymer [108] 97 11 Benzyl/CH2(3-py) NS4 Q dimer [72] 98 CH2(ferrocenyl)/CH2(3-py) NS4 Q dimer [109] 99 12 Et/CH2(4-py) NS4 P polymer [110] 100 13 CH2(ferrocenyl)/CH2(4-py) N2S4 R layer [109] 1 R1 is 2,3-dihydro-1,4-benzodioxin-6-yl)CH2; 2 C2/c polymorph; 3 P21/c polymorph; 4 Pbcn polymorph; 5 P ̄1 polymorph; 6 tetra-acetonitrile solvate; 7 di-hydrate; 8 methanol solvate; 9 R2 is 1,3-benzodioxol-5-CH2; 10 hydrate; 11 ethanol solvate; 12 di-4-methylpyridine solvate; 13 dimethylformamide solvate....

    [...]

  • ...The first, {Zn[S2CN(Et)Ph]2}2, is dimorphic, crystallising in monoclinic (P21/c) and triclinic (P ̄1) space groups, that is, 83 [101] and 84 [102], respectively....

    [...]

Journal Article•DOI•
Dithiocarbamates: Challenges, Control, and Approaches to Excellent Yield, Characterization, and Their Biological Applications.

[...]

Ayodele Temidayo Odularu1, Peter A. Ajibade2•
University of Fort Hare1, University of KwaZulu-Natal2
06 Feb 2019-Bioinorganic Chemistry and Applications
TL;DR: The challenges experienced during the synthesis of dithiocarbamate and mechanisms to overcome them are reviewed in order to obtain accurate results.
Abstract: Progresses made in previous researches on syntheses of dithiocarbamates led to increase in further researches. This paper reviews concisely the challenges experienced during the synthesis of dithiocarbamate and mechanisms to overcome them in order to obtain accurate results. Aspects of its precursor's uses to synthesize adducts, nanoparticles, and nanocomposites are reported. Some common characterization techniques used for the synthesized products were assessed. Biological applications are also reported.

36 citations

Journal Article•DOI•
Synthesis and structural studies of iron sulphide nanocomposites prepared from Fe(III) dithiocarbamates single source precursors

[...]

Athandwe M. Paca1, Peter A. Ajibade1•
University of KwaZulu-Natal1
01 Dec 2017-Materials Chemistry and Physics
TL;DR: In this paper, four Fe(III) dithiocarbamate complexes were synthesized and characterized by spectroscopic techniques and thermogravimetric analysis, and they were used as single source precursors and thermolysed in HDA to prepare iron sulphide nanoparticles.

35 citations

References
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Journal Article•DOI•
A short history of SHELX

[...]

George M. Sheldrick1•
University of Göttingen1
01 Jan 2008-Acta Crystallographica Section A
TL;DR: This paper could serve as a general literature citation when one or more of the open-source SH ELX programs (and the Bruker AXS version SHELXTL) are employed in the course of a crystal-structure determination.
Abstract: An account is given of the development of the SHELX system of computer programs from SHELX-76 to the present day. In addition to identifying useful innovations that have come into general use through their implementation in SHELX, a critical analysis is presented of the less-successful features, missed opportunities and desirable improvements for future releases of the software. An attempt is made to understand how a program originally designed for photographic intensity data, punched cards and computers over 10000 times slower than an average modern personal computer has managed to survive for so long. SHELXL is the most widely used program for small-molecule refinement and SHELXS and SHELXD are often employed for structure solution despite the availability of objectively superior programs. SHELXL also finds a niche for the refinement of macromolecules against high-resolution or twinned data; SHELXPRO acts as an interface for macromolecular applications. SHELXC, SHELXD and SHELXE are proving useful for the experimental phasing of macromolecules, especially because they are fast and robust and so are often employed in pipelines for high-throughput phasing. This paper could serve as a general literature citation when one or more of the open-source SHELX programs (and the Bruker AXS version SHELXTL) are employed in the course of a crystal-structure determination.

81,116 citations

Journal Article•DOI•
Structure validation in chemical crystallography

[...]

Anthony L. Spek1•
Utrecht University1
01 Feb 2009-Acta Crystallographica Section D-biological Crystallography
TL;DR: This paper reports on the current status of structure validation in chemical crystallography and describes the current state of research in this area.
Abstract: Automated structure validation was introduced in chemical crystallography about 12 years ago as a tool to assist practitioners with the exponential growth in crystal structure analyses. Validation has since evolved into an easy-to-use checkCIF/PLATON web-based IUCr service. The result of a crystal structure determination has to be supplied as a CIF-formatted computer-readable file. The checking software tests the data in the CIF for completeness, quality and consistency. In addition, the reported structure is checked for incomplete analysis, errors in the analysis and relevant issues to be verified. A validation report is generated in the form of a list of ALERTS on the issues to be corrected, checked or commented on. Structure validation has largely eliminated obvious problems with structure reports published in IUCr journals, such as refinement in a space group of too low symmetry. This paper reports on the current status of structure validation and possible future extensions.

13,163 citations

Journal Article•DOI•
Probing the Cytotoxicity Of Semiconductor Quantum Dots.

[...]

Austin M. Derfus1, Warren C. W. Chan1, Sangeeta N. Bhatia1•
University of California, San Diego1
01 Jan 2004-Nano Letters
TL;DR: This work found that CdSe-core QDs were indeed acutely toxic under certain conditions and modulated by processing parameters during synthesis, exposure to ultraviolet light, and surface coatings, and suggests that cytotoxicity correlates with the liberation of free Cd2+ ions due to deterioration of the Cd Se lattice.
Abstract: With their bright, photostable fluorescence, semiconductor quantum dots (QDs) show promise as alternatives to organic dyes for biological labeling. Questions about their potential cytotoxicity, however, remain unanswered. While cytotoxicity of bulk cadmium selenide (CdSe) is well documented, a number of groups have suggested that CdSe QDs are cytocompatible, at least with some immortalized cell lines. Using primary hepatocytes as a liver model, we found that CdSe-core QDs were indeed acutely toxic under certain conditions. Specifically, we found that the cytotoxicity of QDs was modulated by processing parameters during synthesis, exposure to ultraviolet light, and surface coatings. Our data further suggest that cytotoxicity correlates with the liberation of free Cd2+ ions due to deterioration of the CdSe lattice. When appropriately coated, CdSe-core QDs can be rendered nontoxic and used to track cell migration and reorganization in vitro. Our results provide information for design criteria for the use of ...

3,236 citations

Journal Article•DOI•
Optical properties of manganese-doped nanocrystals of ZnS.

[...]

R. N. Bhargava1, D. Gallagher1, X. Hong2, Arto V. Nurmikko2•
Philips1, Brown University2
17 Jan 1994-Physical Review Letters
TL;DR: Luminescent measurements show that the efficiency increases with decreasing size of the particles, as expected within the framework of an electron-hole localization theory, suggesting that doped nanocrystals are indeed a new class of materials heretofore unknown.
Abstract: We report for the first time that doped nanocrystals of semiconductor can yield both high luminescent efficiencies and lifetime shortening at the same time. Nanocrystals of Mn-doped ZnS with sizes varying from 3.5 to 7.5 nm were prepared by a room temperature chemical process. These nanosized particles have an external photoluminescent quantum efficiency as high as 18% at room temperature and a luminescent decay at least 5 orders of magnitude faster than the corresponding ${\mathrm{Mn}}^{2+}$ radiative transition in the bulk crystals. Luminescent measurements show that the efficiency increases with decreasing size of the particles, as expected within the framework of an electron-hole localization theory. These results suggest that doped nanocrystals are indeed a new class of materials heretofore unknown.

1,855 citations

Journal Article•DOI•
Applications of Ultrasound to the Synthesis of Nanostructured Materials

[...]

Jin Ho Bang1, Kenneth S. Suslick1•
University of Illinois at Urbana–Champaign1
12 Mar 2010-Advanced Materials
TL;DR: The fundamental principles of both synthetic methods and recent development in the applications of ultrasound in nanostructured materials synthesis are summarized.
Abstract: Recent advances in nanostructured materials have been led by the development of new synthetic methods that provide control over size, morphology, and nano/microstructure. The utilization of high intensity ultrasound offers a facile, versatile synthetic tool for nanostructured materials that are often unavailable by conventional methods. The primary physical phenomena associated with ultrasound that are relevant to materials synthesis are cavitation and nebulization. Acoustic cavitation (the formation, growth, and implosive collapse of bubbles in a liquid) creates extreme conditions inside the collapsing bubble and serves as the origin of most sonochemical phenomena in liquids or liquid-solid slurries. Nebulization (the creation of mist from ultrasound passing through a liquid and impinging on a liquid-gas interface) is the basis for ultrasonic spray pyrolysis (USP) with subsequent reactions occurring in the heated droplets of the mist. In both cases, we have examples of phase-separated attoliter microreactors: for sonochemistry, it is a hot gas inside bubbles isolated from one another in a liquid, while for USP it is hot droplets isolated from one another in a gas. Cavitation-induced sonochemistry provides a unique interaction between energy and matter, with hot spots inside the bubbles of approximately 5000 K, pressures of approximately 1000 bar, heating and cooling rates of >10(10) K s(-1); these extraordinary conditions permit access to a range of chemical reaction space normally not accessible, which allows for the synthesis of a wide variety of unusual nanostructured materials. Complementary to cavitational chemistry, the microdroplet reactors created by USP facilitate the formation of a wide range of nanocomposites. In this review, we summarize the fundamental principles of both synthetic methods and recent development in the applications of ultrasound in nanostructured materials synthesis.

1,501 citations

Related Papers (5)
Group 12 dithiocarbamate complexes: synthesis, spectral studies and their use as precursors for metal sulfides nanoparticles and nanocomposites.

[...]

01 Sep 2013-Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
Peter A. Ajibade, Benjamin C. Ejelonu
Metal complexes of alkyl-aryl dithiocarbamates: Structural studies, anticancer potentials and applications as precursors for semiconductor nanocrystals

[...]

05 Mar 2018-Journal of Molecular Structure
Fartisincha P. Andrew, Peter A. Ajibade
A short history of SHELX

[...]

01 Jan 2008-Acta Crystallographica Section A
George M. Sheldrick
Synthesis, characterization and anticancer studies of bis(1-phenylpiperazine dithiocarbamato) Cu(II), Zn(II) and Pt(II) complexes: Crystal structures of 1-phenylpiperazine dithiocarbamato-S,S′ zinc(II) and Pt(II)

[...]

15 Oct 2018-Journal of Molecular Structure
Fartisincha P. Andrew, Peter A. Ajibade
Metal-dithiocarbamate complexes: chemistry and biological activity.

[...]

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