were harvested from a dry acetonitrile solution of Cd[S 2 CN(iPr)-CH 2 CH 2 OH] 2 after one or two days and proved to be a coordination polymer in which all dithiocarbamate ligands are μ 2 ,κ 2 -tridentate, bridging two cadmium atoms and simultaneously chelating one of these. If the same solution was allowed to stand for at least several days, 2 is replaced by blocks comprising a supramolecular isomer of 2, dimeric 1, with formula {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 •2H 2 O•2MeCN, and two ligands coordinating μ 2 ,κ 2 as in 2 and the other two purely κ 2 -chelating. The time dependency correlates with the pivotal role of water in driving the conversion of "chain" 2 to "ball" 1; crystals of 2 could not be isolated from "wet" acetonitrile. When each of 1 and 2 are dissolved in solution, they exhibit comparable spectroscopic attributes ( 1 H, 13 C, and 113 Cd NMR and UV/vis), indicating the solution structures are the same. Both 1 and 2 are luminescent in the solid state with 1 being significantly brighter than 2. Greenockite CdS nanoparticles are generated by the thermal decomposition of both 1 and 2.

Exploring the crystallization landscape of cadmium bis (N-hydroxyethyl, N-isopropyldithiocarbamate) dithiocarbamate ligands. In each of 3 and 4 the binuclear {Cd[S2CN(iPr)CH2CH2OH]2}2 SI, as in 2, is observed strongly suggesting a thermodynamic preference for this form.

Four binuclear phosphanesilver(I) dithiocarbamates, {cyclohexyl 3 PAg(S 2 CNRR′)} 2 for R = R′ = Et (1), CH 2 CH 2 (2), CH 2 CH 2 OH (3) and R = Me, R′ = CH 2 CH 2 OH (4) have been synthesised and characterised by spectroscopy and crystallography, and feature tri-connective, μ 2 -bridging dithiocarbamate ligands and distorted tetrahedral geometries based on PS 3 donor sets. The compounds were evaluated for anti-bacterial activity against a total of 12 clinically important pathogens. Based on minimum inhibitory concentration (MIC) and cell viability tests (human embryonic kidney cells, HEK 293), 1-4 are specifically active against Gram-positive bacteria while demonstrating low toxicity; 3 and 4 are active against methicillin resistant S. aureus (MRSA). Across the series, 4 was most effective and was more active than the standard anti-biotic chloramphenicol. Time kill assays reveal 1-4 to exhibit both time-and concentration-dependent pharmacokinetics against susceptible bacteria. Compound 4 demonstrates rapid (within 2 h) bactericidal activity at 1 and 2 × MIC to reach a maximum decrease of 5.2 log 10 CFU/mL against S. aureus (MRSA). While the R = Cy and Ph derivatives exhibited specific activity against Gram-positive bacteria, the R = Et compound showed broad range activity against both Gram-positive and Gram-negative bacteria [23]. Also, based on time kill studies the R = Cy and Ph compounds were bactericidal whereas the R = Et compound was bactericidal and

The incorporation of dithiocarbamate ligands in the preparation of metal complexes is largely prompted by the versatility of this molecule. Fascinating coordination chemistry can be obtained from the study of such metal complexes ranging from their preparation, the solid-state properties, solution behavior as well as their applications as bioactive materials and luminescent compounds, to name a few. In this overview, the dithiocarbamate complexes of platinum-group elements form the focus of the discussion. The structural aspects of these complexes will be discussed based upon the intriguing findings obtained from their solid- (crystallographic) and solution-state (NMR) studies. At the end of this review, the applications of platinum-group metal complexes will be discussed.

Abstract. The presence of both κ 2 -chelating and µ2,κ 2

In the solid state each of three binuclear zinc dithiocarbamates bearing hydroxyethyl groups, {Zn[S2CN(R)CH2CH2OH]2}2 for R = iPr (1), CH2CH2OH (2), and Me (3), and an all alkyl species, [Zn(S2CNEt2)2]2 (4), features a centrosymmetric {ZnSCS}2 core with a step topology; both 1 and 3 were isolated as monohydrates. All compounds were broadly cytotoxic, specifically against human cancer cell lines compared with normal cells, with greater potency than cisplatin. Notably, some selectivity were indicated with 2 being the most potent against human ovarian carcinoma cells (cisA2780), and 4 being more cytotoxic toward multidrug resistant human breast carcinoma cells (MCF-7R), human colon adenocarcinoma cells (HT-29), and human lung adenocarcinoma epithelial cells (A549). Based on human apoptosis PCR-array analysis, caspase activities, DNA fragmentation, cell apoptotic assays, intracellular reactive oxygen species (ROS) measurements and human topoisomerase I inhibition, induction of apoptosis in HT-29 cells is demonstrated via both extrinsic and intrinsic pathways. Compounds 2-4 activate the p53 gene while 1 activates both p53 and p73. Cell cycle arrest at the S and G2/M phases correlates with inhibition of HT-29 cell growth. Cell invasion is also inhibited by 1-4 which is correlated with down-regulation of NF-κB.

The influence of C–H⋯π(PdS2C) interactions in the molecular packing of Pd(S2COR)2increases as the steric bulk ofRincreases.

Four polymorphs are described for the one-dimensional coordination polymer {Cd[S2P(OMe)2]2(4-pyridine-aldazine)}n (1) which features a trans-N2S4 distorted octahedral coordination geometry. Lattice energy calculations show the room temperature form, 1α, is the thermodynamically stable phase, being 1.52 kcal/mol more stable than the 1β form per unit formula. The latter is formed at 233 K on cooling 1α based on single crystal data. Single crystals of forms 1α and 1β exhibit a reversible single-crystal-single-crystal phase change which also 2 occurs in the bulk form as seen in DSC and PXRD experiments. When 1 was "snap frozen" at 100 K under a cold stream, 1β was observed most of the time but sometimes forms 1γ and 1δ were found. When warmed, 1β converted to 1α by 293 K, and each of 1γ and 1δ first converted to 1β (120-130 and 140-150 K, respectively) and then to 1α (280 K), correlating with the calculated lattice energies; subsequent cooling only yielded 1β, indicating 1γ and 1δ are metastable forms.The polymorphs exhibit different molecular packing patterns based on different non-covalent interactions and these have been evaluated by Hirshfeld surface analyses and NCI plots. 1. ASSOCIATED CONTENTSupporting Information Available. Crystallographic data for 1α-1δ in CIF format, geometric data, intermolecular interaction distances, Hirshfeld surface images, DSC, and PXRD patterns. This material is available free of charge via the Internet at http://pubs.acs.org.