Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond
10 Sep 2021-Vol. 9, Iss: 9, pp 70
TL;DR: Copper dithiocarbamates 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 as mentioned in this paper.
Abstract: 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 A. 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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01 Feb 2016
TL;DR: There has been a surge of activity, based on a great deal of mechanistic information, aimed at developing nonclassical platinum complexes that operate via mechanisms of action distinct from those of the approved drugs.
Abstract: The platinum drugs, cisplatin, carboplatin, and oxaliplatin, prevail in the treatment of cancer, but new platinum agents have been very slow to enter the clinic. Recently, however, there has been a surge of activity, based on a great deal of mechanistic information, aimed at developing nonclassical platinum complexes that operate via mechanisms of action distinct from those of the approved drugs. The use of nanodelivery devices has also grown, and many different strategies have been explored to incorporate platinum warheads into nanomedicine constructs. In this Review, we discuss these efforts to create the next generation of platinum anticancer drugs. The introduction provides the reader with a brief overview of the use, development, and mechanism of action of the approved platinum drugs to provide the context in which more recent research has flourished. We then describe approaches that explore nonclassical platinum(II) complexes with trans geometry or with a monofunctional coordination mode, polynuclea...
39 citations
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TL;DR: In this paper , two facile, low-temperature and inexpensive techniques (solventless thermolysis and aerosol-assisted chemical vapor deposition (AACVD)) for the preparation of binary digenite (Cu1.8S), chalcocite (cu2S) and stibnite (Sb2S3) and several phases of ternary copper-antimony-sulfide (Cu2xSb 2(1-x)Sy, where 0 ≤ x ≤ 1).
Abstract: Copper antimony sulfide (Cu-Sb-S) has recently been proposed as an attractive alternative photovoltaic material due to the earth-abundant and non-toxic nature of the elements, high absorption coefficients and band gaps commensurate with efficient harvesting of solar photonic flux across multiple phases of Cu-Sb-S. These materials are therefore highly desirable and sustainable and scalable deposition techniques to produce them are of interest. In this paper, we demonstrate two facile, low-temperature and inexpensive techniques (solventless thermolysis and aerosol-assisted chemical vapor deposition (AACVD)) for the preparation of binary digenite (Cu1.8S), chalcocite (Cu2S) and stibnite (Sb2S3) and several phases of ternary copper-antimony-sulfide (Cu2xSb2(1-x)Sy, where 0 ≤ x ≤ 1). It was found that by utilising these different techniques and varying the ratio of Cu:Sb, pure phases of ternary chalcostibite (CuSbS2), fematinite (Cu3SbS4) and tetrahedrite (Cu12Sb4S13) can be achieved. Two single-source precursors were investigated for this purpose, namely the diethyldithiocarbamate (DTC) complexes of copper and antimony Cu(DTC)2 and Sb(DTC)3. These were decomposed both individually (to produce binary materials) and combined (to produce ternary materials) at different ratios. From the solventless thermolysis and AACVD methods, either particulate or thin film material was formed, respectively. These materials were then characterised by powder XRD, SEM, EDX and Raman spectroscopies to determine the crystalline phase, material morphology and uniformity of elemental composition. This analysis demonstrated that as the Cu-content increases, the phase of the ternary material changes from chalcostibite (CuSbS2) and fematinite (Cu3SbS4) at a low Cu:Sb ratio to tetrahedrite (Cu12Sb4S13) at a high Cu:Sb ratio.
9 citations
01 Jan 2009
TL;DR: A new mononuclear Cu(Ⅱ) dithiocarbamate complex was synthesized and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction as discussed by the authors.
Abstract: A new mononuclear Cu(Ⅱ) dithiocarbamate complex CuI(prdtc)(phen) 1(prdtc = N-pyrrolidinyldithiocarbamate,phen = 1,10-phenanthroline) was synthesized and characterized by elemental analysis,IR spectrum,and single-crystal X-ray diffraction.The crystal belongs to the monoclinic system,space group P21/c with a = 8.7110(9),b = 14.7143(14),c = 14.8507(15) ,β = 109.721(6)o,V = 1791.9(3) 3,Z = 4,Dc = 1.916 g/cm3,C17H16CuIN3S2,Mr = 516.89,λ(MoKa) = 0.71073 ,μ = 3.178 mm-1,F(000) = 1012,the final R = 0.0369 and wR = 0.0987.A total of 4082 unique reflections were collected,of which 2916 with I 2σ(I) were observed.The Cu(Ⅱ) atom is five-coordinated in a distorted square-pyramidal geometry by one I atom in the apical position,two S atoms from a prdtc ligand and two N atoms from a phen ligand in the basal plane.There exist face-to-face aromatic π-π stacking interactions between adjacent phen ligands stabilizing the structure and making the complex assemble into a 1D structure along the a axis.It can be concluded that the difference of the dtc flexibility and reaction conditions result in the structural difference between complex 1 and CuI(dmdtc)(phen)(dmdtc = N,N-dimethyldithiocarbamate).
5 citations
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TL;DR: In this paper , the reaction of potassium (aza-15-crown-5)dithiocarbamate (KO4NCS2) and (Me2S)AuCl gave the dinuclear complex [Au(O4 NCS2)]2.
Abstract: The reaction of potassium (aza-15-crown-5)dithiocarbamate (KO4NCS2) and (Me2S)AuCl gave the dinuclear complex [Au(O4NCS2)]2, which underwent structural transformation upon heating to rearrange into the hexanuclear complex [Au(O4NCS2)]6. Under similar reaction conditions, KO4NCS2 reacted with AgNO3 or [Cu(CH3CN)4]ClO4 to give the 1-D coordination polymer [Ag(O4NCS2)]n (1) and the tetranuclear complex [Cu(O4NCS2)]4 (2), respectively. It is noted that upon heating a similar structural transformation process occurs from tetranuclear complex 2 to the octanuclear complex [Cu(O4NCS2)]8 (2'), connected by a weak Cu⋯S contact of 2.846 Å, and it has been isolated and corroborated by powder and single-crystal X-ray diffraction studies as well. Moreover, a variety of MO4NCS2 salts (M = Li+, Na+, K+ and Rb+) were used to react with AgNO3 to construct a series of coordination architectures: [LiAg(O4NCS2)2(μ-H2O)0.5]2 (3), {Na[Ag(O4NCS2)2]}n (4), {K[Ag(O4NCS2)2]}n (5) and {Rb[Ag(O4NCS2)2]}n (6). The smallest Li+ ion only coordinates with four oxygen atoms from the same azacrown ether ring and one H2O molecule, leading to a 1-D hydrogen-bonded chain with another azacrown ether ring for complex 3. The larger Na+ ion coordinates with seven oxygen atoms from two different crown ether rings, leading to a 1-D chain for complex 4. However, the largest K+ and Rb+ ions constitute a 1-D framework, except that each metal ion coordinates with eight oxygen atoms from two different crown ether rings, featuring a 1-D helical chain for complexes 5 and 6. Hence, the different sizes of alkaline metal ions exert a dramatic effect on the structural motifs of complexes 3-6. Remarkably, the dithiocarbamate moieties adopt μ2-bridging ([Au(O4NCS2)]2 and [Au(O4NCS2)]6), μ3- and μ4-bridging (1-2) and chelate forms (3-6) in the structural backbones.
3 citations
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TL;DR: In this paper , the crystal structures of complexes 1, 3 and 4 were determined by single crystal X-ray diffraction and showed that the dithiocarbamate ligands are coordinated to the nickel atom in the bidentate manner and the central atom is four coordinated.
2 citations
References
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TL;DR: Recently, there has been a surge of activity, based on a great deal of mechanistic information, aimed at developing nonclassical platinum complexes that operate via mechanisms of action distinct from those of the approved drugs as mentioned in this paper.
Abstract: The platinum drugs, cisplatin, carboplatin, and oxaliplatin, prevail in the treatment of cancer, but new platinum agents have been very slow to enter the clinic. Recently, however, there has been a surge of activity, based on a great deal of mechanistic information, aimed at developing nonclassical platinum complexes that operate via mechanisms of action distinct from those of the approved drugs. The use of nanodelivery devices has also grown, and many different strategies have been explored to incorporate platinum warheads into nanomedicine constructs. In this Review, we discuss these efforts to create the next generation of platinum anticancer drugs. The introduction provides the reader with a brief overview of the use, development, and mechanism of action of the approved platinum drugs to provide the context in which more recent research has flourished. We then describe approaches that explore nonclassical platinum(II) complexes with trans geometry or with a monofunctional coordination mode, polynuclea...
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TL;DR: It is shown that dithiocarbamates and metal chelators can potently block the activation of nuclear factor kappa B (NF-kappa B), a transcription factor involved in human immunodeficiency virus type 1 (HIV-1) expression, signaling, and immediate early gene activation during inflammatory processes.
Abstract: Dithiocarbamates and iron chelators were recently considered for the treatment of AIDS and neurodegenerative diseases. In this study, we show that dithiocarbamates and metal chelators can potently block the activation of nuclear factor kappa B (NF-kappa B), a transcription factor involved in human immunodeficiency virus type 1 (HIV-1) expression, signaling, and immediate early gene activation during inflammatory processes. Using cell cultures, the pyrrolidine derivative of dithiocarbamate (PDTC) was investigated in detail. Micromolar amounts of PDTC reversibly suppressed the release of the inhibitory subunit I kappa B from the latent cytoplasmic form of NF-kappa B in cells treated with phorbol ester, interleukin 1, and tumor necrosis factor alpha. Other DNA binding activities and the induction of AP-1 by phorbol ester were not affected. The antioxidant PDTC also blocked the activation of NF-kappa B by bacterial lipopolysaccharide (LPS), suggesting a role of oxygen radicals in the intracellular signaling of LPS. This idea was supported by demonstrating that treatment of pre-B and B cells with LPS induced the production of O2- and H2O2. PDTC prevented specifically the kappa B-dependent transactivation of reporter genes under the control of the HIV-1 long terminal repeat and simian virus 40 enhancer. The results from this study lend further support to the idea that oxygen radicals play an important role in the activation of NF-kappa B and HIV-1.
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TL;DR: In this article, the authors describe localized surface plasmon resonances arising from p-type carriers in vacancy-doped semiconductor quantum dots (QDs) and demonstrate that doped QDs allow realization of LSPRs and quantum-confined excitons within the same nanostructure.
Abstract: Localized surface plasmon resonances (LSPRs) typically arise in nanostructures of noble metals resulting in enhanced and geometrically tunable absorption and scattering resonances. LSPRs, however, are not limited to nanostructures of metals and can also be achieved in semiconductor nanocrystals with appreciable free carrier concentrations. Here, we describe well-defined LSPRs arising from p-type carriers in vacancy-doped semiconductor quantum dots (QDs). Achievement of LSPRs by free carrier doping of a semiconductor nanocrystal would allow active on-chip control of LSPR responses. Plasmonic sensing and manipulation of solid-state processes in single nanocrystals constitutes another interesting possibility. We also demonstrate that doped semiconductor QDs allow realization of LSPRs and quantum-confined excitons within the same nanostructure, opening up the possibility of strong coupling of photonic and electronic modes, with implications for light harvesting, nonlinear optics, and quantum information processing.
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TL;DR: In this article, the authors describe localized surface plasmon resonance (LSPR) arising from p-type carriers in vacancy-doped semiconductor quantum dots, which opens up possibilities for light harvesting, nonlinear optics, optical sensing and manipulation of solid-state processes in single nanocrystals.
Abstract: Quantum confinement of electronic wavefunctions in semiconductor quantum dots (QDs) yields discrete atom-like and tunable electronic levels, thereby allowing the engineering of excitation and emission spectra. Metal nanoparticles, on the other hand, display strong resonant interactions with light from localized surface plasmon resonance (LSPR) oscillations of free carriers, resulting in enhanced and geometrically tunable absorption and scattering resonances. The complementary attributes of these nanostructures lends strong interest toward integration into hybrid nanostructures to explore enhanced properties or the emergence of unique attributes arising from their interaction. However, the physicochemical interface between the two components can be limiting for energy transfer and synergistic coupling within such a hybrid nanostructure. Therefore, it is advantageous to realize both attributes, i.e., LSPRs and quantum confinement within the same nanostructure. Here, we describe well-defined LSPRs arising from p-type carriers in vacancy-doped semiconductor quantum dots. This opens up possibilities for light harvesting, non-linear optics, optical sensing and manipulation of solid-state processes in single nanocrystals.
1,159 citations