Functionalization of Polymer-Wrapped Silver Nanoclusters and Potential Applications as Antimicrobial Mask Materials.

The poly(methacrylic acid) (PMAA) polymer stabilized silver nanoclusters Agn (n = 2-9), synthesized in aqueous solution by the selected light wavelength irradiation photolysis approach, have been functionalized with thiol and amine ligands and successfully transferred from aqueous to organic media. Low- or high-resolution positive mass spectra showed constant species composites with the molecular formula AgnLn-1 [n = 2 to ∼9, L = butylmercaptan (C4H9S), thiolphenol (C6H5S), or dodecanethiol (C12H25S)] and proved that the molecules consist of deprotonated sulfur ligands in each species with one positive charge. Fourier transform infrared and X-ray photoelectron spectroscopy are consistent, indicating deprotonated sulfur, while silver has a zero valence value. The composition of the functionalized silver clusters is in agreement with that observed from polymer-wrapped "naked" silver clusters, which strongly indicates their real existence. For the silver cluster amine systems (heptylamine, dodecylamine, and oleylamine), only "naked" silver cluster species were detected from mass spectroscopy, similar to the polymer-wrapped case, indicating they are not stable enough in the gas phase. The development of a new antibacterial mask material is very important. The dodecylamine-capping silver nanoclusters were selected by coating the coffee filter surface to conduct antibacterial tests with Staphylococcus aureus and Escherichia coli, demonstrating very efficient antimicrobial properties even with organic capping ligands. Experiments also show that they work on mask material. One nanowire assembly with polystyrene and dodecylamine-capping silver nanoclusters was prepared, showing uniform nanofibers generated via the electrospray technique.

Effect of size and surface chemistry of gold nanoparticles on their retention in a sediment-water system and Lumbriculus variegatus.

With the increased production, usage, and disposal of engineered nanoparticles (ENPs), there is growing concern over the fate of ENPs in the environment, their potential bioavailability and ecotoxicity. It is assumed that bioavailability and uptake into organisms depend on the environmental conditions as well as the physicochemical properties of ENPs, such as particle size or surface coating. A major sink for nanoparticles is expected to be sediments due to sorption and agglomeration processes. Accordingly, this study, investigated how different sizes (5 and 30 nm) and surface coatings of three different AuENPs based on citrate (AuCIT), mercaptoundecanoic acid (AuMUDA), and bovine serum albumin (AuBSA) affected the retention of ENPs in a sediment-water system and subsequent uptake into sediment-dwelling organism Lumbriculus variegatus (L. variegatus). Surface charge was found to be one of the factors affecting retention of the AuENPs in the sediment-water system. More negatively charged AuENPs had a higher mass fraction in the supernatant after 24 h exposure. Furthermore, the stability of AuENPs in the supernatant depended more on their zeta potential than particle size (5 nm vs. 30 nm). The surface coating was found to play an important role in the uptake (after depuration) of Au in L. variegatus, that is, AuBSA > AuCIT > AuMUDA.

Alloyed Crystalline CdSe1-xSx Semiconductive Nanomaterials - A Solid State 113Cd NMR Study.

Solid-state NMR analysis on wurtzite alloyed CdSe1-xSx crystalline nanoparticles and nanobelts provides evidence that the 113Cd NMR chemical shift is not affected by the varying sizes of nanoparticles, but is sensitive to the S/Se anion molar ratios. A linear correlation is observed between 113Cd NMR chemical shifts and the sulfur component for the alloyed CdSe1-xSx (0

Monochromatic Photolysis to Generate Silver Quantum Clusters in Polymer Matrices with Efficiently Antibio Property.

Size-control of species via wavelength to selectively synthesize Ag quantum clusters (QCs) was utilized and the synthesis conditions of this system (AgNO3, poly(methacrylic acid) (PMAA) with light) were optimized by changing a variety of parameters. Silver QCs, stabilized by PMAA with different compositions, have been synthesized in aqueous solution by tuning the irradiation monochromatic light wavelengths (300 or 365 nm) and AgNO3/MAA ratio (1 or 2). The novel preparation procedure has demonstrated a new approach to enlarge the population of the Ag QC family and proved the effectiveness of size control to prepare Ag QCs by tuning the light wavelength. Naked Ag QC species Agn (n = 2-9, 11, and 13) in polymer matrices are fully characterized by mass spectrometer, thus providing finger-printing evidence of their presence. Details regarding the photolysis reaction procedure, Ag QC optical properties, and the origins of fluorescence are discussed. Through a combination of results obtained from mass spectroscopy, fluorescence, and time-dependent density functional theory, we can assign the origin of fluorescence from a small silver cluster of Ag2 in organic scaffolds. The kinetics of the photolysis reaction follows first-order kinetics (k = 0.1/h). After thiolphenol (C6H5SH) ligand functionalization of the generated silver clusters in aqueous solution, the low or high resolution mass spectra showed the constant species composites with a molecular formula AgnLn-1 (n = 2-9 and L = C6H5S). More evidence indicated the formation of polymer-wrapped silver clusters. Their antibio property was explored, and we confirmed that they indeed show efficient activity.

Application of nanoparticle tracking analysis for characterising the fate of engineered nanoparticles in sediment-water systems.

Novel applications of nanotechnology may lead to the release of engineered nanoparticles (ENPs), which result in concerns over their potential environmental hazardous impact. It is essential for the research workers to be able to quantitatively characterise ENPs in the environment and subsequently to assist the risk assessment of the ENPs. This study hence explored the application of nanoparticle tracking system (NTA) to quantitatively describe the behaviour of the ENPs in natural sediment-water systems. The NTA allows the measurement of both particle number concentration (PNC) and particle size distribution (PSD) of the ENPs. The developed NTA method was applied to a range of gold and magnetite ENPs with a selection of surface properties. The results showed that the positively-charged ENPs interacted more strongly with the sediment than neutral and negatively-charged ENPs. It was also found that the citrate coated Au ENPs had a higher distribution percentage (53%) than 11-mercaptoundecanoic acid coated Au ENPs (20%) and citrate coated magnetite ENPs (21%). The principles of the electrostatic interactions between hard (and soft) acids and bases (HSAB) are used to explain such behaviours; the hard base coating (i.e. citrate ions) will interact more strongly with hard acid (i.e. magnetite) than soft acid (i.e. gold). The results indicate that NTA is a complementary method to existing approaches to characterise the fate and behaviour of ENPs in natural sediment.

Do particle size and surface functionality affect uptake and depuration of gold nanoparticles by aquatic invertebrates?

Because of the widespread use of engineered nanoparticles (ENPs) in consumer and industrial products, it is inevitable that these materials will enter the environment. It is often stated that the uptake of ENPs into organisms in the environment is related to the particle size and surface functionality. To test this assumption, the present study investigated the uptake and depuration of gold nanoparticle (Au NPs) coated with either citrate (Au-citrate NPs), mercaptoundecanoic acid (Au-MUDA NPs), amino polyethylene glycol (PEG) thiol (Au-NH2 NPs), or PEG (Au-PEG NP) by the aquatic invertebrate Gammarus pulex. The studies were performed using a range of standard ecotoxicity media and natural waters, resulting in varying degrees of aggregation of the different NPs. Uptake of gold by G. pulex varied depending on the surface coatings, with Au-MUDA and Au-citrate NPs being taken up to a greater extent than Au-NH2 and Au-PEG NPs in all test media and natural waters. In all test media evaluated, higher amounts of amino and PEG-coated ENPs were eliminated compared with MUDA- and citrate-coated ENPs. No obvious relationships were seen between the aggregation state of the different Au NPs in treatment and uptake, suggesting that the widely accepted assumption that Au NP uptake is related to particle size does not hold for the range of aggregation states studied (67.1-178.8 nm). Positive correlations between particle number concentration in the media and uptake were observed, indicating that this factor might partly explain the differences in uptake of a particle from different media types.

Widespread nanoparticle-assay interference: implications for nanotoxicity testing.

The evaluation of engineered nanomaterial safety has been hindered by conflicting reports demonstrating differential degrees of toxicity with the same nanoparticles. The unique properties of these materials increase the likelihood that they will interfere with analytical techniques, which may contribute to this phenomenon. We tested the potential for: 1) nanoparticle intrinsic fluorescence/absorbance, 2) interactions between nanoparticles and assay components, and 3) the effects of adding both nanoparticles and analytes to an assay, to interfere with the accurate assessment of toxicity. Silicon, cadmium selenide, titanium dioxide, and helical rosette nanotubes each affected at least one of the six assays tested, resulting in either substantial over- or under-estimations of toxicity. Simulation of realistic assay conditions revealed that interference could not be predicted solely by interactions between nanoparticles and assay components. Moreover, the nature and degree of interference cannot be predicted solely based on our current understanding of nanomaterial behaviour. A literature survey indicated that ca. 95% of papers from 2010 using biochemical techniques to assess nanotoxicity did not account for potential interference of nanoparticles, and this number had not substantially improved in 2012. We provide guidance on avoiding and/or controlling for such interference to improve the accuracy of nanotoxicity assessments.

Regulatory ecotoxicity testing of engineered nanoparticles: are the results relevant to the natural environment?

Engineered nanoparticles (ENPs) will be released to the environment during use or following the disposal of ENP-containing products and concerns have been raised over the risks of ENPs to the environment. Many studies have explored the toxicity of ENPs to aquatic organisms but these studies have usually been performed with little understanding of the ENPs' behaviour in the test media and the relationship between behaviour in the media to behaviour in natural waters. This study evaluated and compared the aggregation behaviour of four model gold nanoparticle (NP) types (coated with neutral, negative, positive and amphoteric cappings) in standard ecotoxicity test media and natural waters. The effects of humic acid (HA) and test organisms on aggregation were also investigated. In standard media, positive and neutral NPs were stable, whereas amphoteric and negative NPs generally showed substantial aggregation. In natural waters, amphoteric NPs were generally found to be stable, neutral and positive NPs showed substantial aggregation while negative NPs were stable in some waters and unstable in others. HA addition stabilised the amphoteric NPs, destabilised the positive NPs and had no effect on stability of negative NPs. The presence of invertebrates generally lowered the degree of particle aggregation while macrophytes had no effect. Given the dramatically different behaviours of ENPs in various standard media and natural waters, current regulatory testing may either under- or overestimate the toxicity of nanomaterials to aquatic organisms. Therefore, there is a pressing need to employ ecotoxicity media which better represent the behaviour of ENPs in natural system.

Mechanistic insights into the effect of nanoparticles on zebrafish hatch.

Aquatic organisms are susceptible to waterborne nanoparticles (NP) and there is only limited understanding of the mechanisms by which these emerging contaminants may affect biological processes. This study used silicon (nSi), cadmium selenide (nCdSe), silver (nAg) and zinc NPs (nZnO) as well as single-walled carbon nanotubes (SWCNT) to assess NP effects on zebrafish (Danio rerio) hatch. Exposure of 10 mg/L nAg and nCdSe delayed zebrafish hatch and 100 mg/L of nCdSe as well as 10 and 100 mg/L of uncoated nZnO completely inhibited hatch and the embryos died within the chorion. Both the morphology and the movement of the embryos were not affected, and it was determined that the main mechanism of hatch inhibition by NPs is likely through the interaction of NPs with the zebrafish hatching enzyme. Furthermore, it was concluded that the observed effects arose from the NPs themselves and not their dissolved metal components.

Disruption of biomolecule function by nanoparticles: how do gold nanoparticles affect Phase I biotransformation of persistent organic pollutants?

The potential influence of nanoparticles on cytochrome P-450 (CYP) isozyme mediated Phase I biotransformation of persistent organic pollutants (POPs) in vitro was investigated using citrate-capped gold nanoparticles (AuNPs) and 2,2',3,5',6-pentachlorobiphenyl (PCB 95) as the probe nanoparticle and compound, respectively. AuNPs affected the biotransformation activity of rat CYP2B1 and changed the atropisomeric composition of PCB 95, depending on the incubation time and the AuNP concentration. Electrostatic repulsion between citrate-coated AuNPs and rat CYP2B1 may influence the active conformation of the isozyme and consequently affect its activity and stereoselectivity. In addition, the effects of AuNPs on rat CYP2B1 activity also appeared to be through interference with the CYP catalytic cycle's electron transfer chain. Incubations with AuNPs had a decline in buffer conductance and an absorbance band red shift of AuNPs, from electrostatic interactions of K(+) with negatively-charged AuNP aggregates. These ionic strength changes affected the formation rate of nicotinamide adenine dinucleotide phosphate, which provides electrons for the oxidative reaction cycle, and the biotransformation activity and stereoselectivity of CYP. This study suggests that charged nanoparticles may be able to alter the functions of biomolecules directly, by electrostatic interaction, or indirectly, by changes to the surrounding ionic strength. These factors should be taken into account for further understanding and prediction of the environmental behavior and fate of POPs and nanoparticles.

An investigation of 1:1 adducts of gallium trihalides with triarylphosphines by solid-state (69/71)Ga and 31P NMR spectroscopy.

Several 1:1 adducts of gallium trihalides with triarylphosphines, X(3)Ga(PR(3)) (X=Cl, Br, and I; PR(3)=triarylphosphine ligand), were investigated by using solid-state (69/71)Ga and (31)P NMR spectroscopy at different magnetic-field strengths. The (69/71)Ga nuclear quadrupolar coupling parameters, as well as the gallium and phosphorus magnetic shielding tensors, were determined. The magnitude of the (71)Ga quadrupolar coupling constants (C(Q)((71)Ga)) range from approximately 0.9 to 11.0 MHz. The spans of the gallium magnetic shielding tensors for these complexes, δ(11)-δ(33), range from approximately 30 to 380 ppm; those determined for phosphorus range from 10 to 40 ppm. For any given phosphine ligand, the gallium nuclei are most shielded for X=I and least shielded for X=Cl, a trend previously observed for In(III)-phosphine complexes. This experimental trend, attributed to spin-orbit effects of the halogen ligands, is reproduced by DFT calculations. The signs of C(Q)((69/71)Ga) for some of the adducts were determined from the analysis of the (31)P NMR spectra acquired with magic angle spinning (MAS). The (1)J((69/71)Ga,(31)P) and ΔJ((69/71)Ga, (31)P) values, as well as their signs, were also determined; values of (1)J((71)Ga,(31)P) range from approximately 380 to 1590 Hz. Values of (1)J((69/71)Ga,(31)P) and ΔJ((69/71)Ga,(31)P) calculated by using DFT have comparable magnitudes and generally reproduce experimental trends. Both the Fermi-contact and spin-dipolar Fermi-contact mechanisms make important contributions to the (1)J((69/71)Ga,(31)P) tensors. The (31)P NMR spectra of several adducts in solution, obtained as a function of temperature, are contrasted with those obtained in the solid state. Finally, to complement the analysis of NMR spectra for these adducts, single-crystal X-ray diffraction data for Br(3)Ga[P(p-Anis)(3)] and I(3)Ga[P(p-Anis)(3)] were obtained.

Silver nanoparticles inhibit sodium uptake in juvenile rainbow trout (Oncorhynchus mykiss).

The silver ion (Ag(+)) is well documented to be a potent inhibitor of sodium (Na(+)) transport in fish. However, it has not been determined whether silver nanoparticles (Ag NPs) elicit this same effect and, if so, if the NP itself and/or the dissociation of ionic Ag(+) causes this effect. Citrate-capped Ag NPs were dialyzed in water to determine the dissolution rate of ionic Ag(+) from the NPs and the maximum concentration of free Ag(+) released from the NPs was used as a paired Ag(+) control to distinguish NP effects from ionic metal effects. The maximum concentration of ionic Ag(+) released from these NPs over 48 h was 0.02 µg l(-1). Juvenile rainbow trout were exposed to 1.0 mg l(-1) citrate-capped Ag NPs and dialyzed citrate-capped Ag NPs or 10 µg l(-1) and 0.02 µg l(-1) ionic Ag(+) (as AgNO(3)) as controls. Both nondialyzed and dialyzed Ag NPs and 10 µg l(-1) ionic Ag(+) significantly inhibited unidirectional Na(+) influx by over 50% but had no effect on unidirectional Na(+) efflux. Na(+),K(+)-ATPase was significantly inhibited by the Ag NPs with no discernible effect on carbonic anhydrase activity. This study is the first to show that sodium regulation is disrupted by the presence of citrate-capped Ag NPs, and the results suggest that there are nanospecific effects.

Influence of surface functionalization and particle size on the aggregation kinetics of engineered nanoparticles.

In an effort to minimize the impact on the environment or improve the properties of choice, most engineered nanoparticles used for commercial applications are surface functionalized. The release of these functionalized engineered nanoparticles (FENPs) into the environment can be either deliberate or accidental. Scientific research to date has tended to focus on evaluating the toxicity of FENPs, with less attention being given to exposure assessments or to the study of their general behavior in natural environments. We have therefore investigated the effects of environmental parameters such as pH, NaCl concentration, and natural organic matter concentration on the aggregation kinetics of FENPs with time resolved dynamic light scattering, using functionalized gold nanoparticles (FAuNPs) as a representative of these particles. We also investigated the effects of average particle size, the type of surface capping agent, and particle concentration on FAuNP aggregation kinetics. Our results show that the physico-chemical properties of the capping agent have a greater influence on the aggregation behavior of FAuNPs than either their core composition or their particle size.

Inhibition of enzyme activity by nanomaterials: potential mechanisms and implications for nanotoxicity testing.

The objective of this study was to investigate whether nanoparticle-exposure affects enzyme function and to determine the mechanisms responsible. Silicon, Au, and CdSe nanoparticles were synthesized in house and their physicochemical properties were characterized. The activity of purified lactate dehydrogenase (LDH) was inhibited or abolished by all nanoparticles tested. Inhibition was dependent upon particle core and surface-functional group composition. Inhibition of LDH was absent in crude tissue homogenates, in the presence of albumin, and at the isoelectric point of the protein, indicating that nanoparticles bind non-specifically to abundant proteins via a charge interaction. Circular dichroism spectroscopy suggests that the structure of LDH may be altered by nanoparticles in a manner different from that of bulk controls. We present new data on the specific physicochemical properties of nanoparticles that may lead to bioactivity and highlight a number of potentially serious problems with common nanotoxicity testing methods.

Actinide metals with multiple bonds to carbon: synthesis, characterization, and reactivity of U(IV) and Th(IV) bis(iminophosphorano)methandiide pincer carbene complexes.

Treatment of ThCl(4)(DME)(2) or UCl(4) with 1 equiv of dilithiumbis(iminophosphorano) methandiide, [Li(2)C(Ph(2)P═NSiMe(3))(2)] (1), afforded the chloro actinide carbene complexes [Cl(2)M(C(Ph(2)P═NSiMe(3))(2))] (2 (M = Th) and 3 (M = U)) in situ. Stable PCP metal-carbene complexes [Cp(2)Th(C(Ph(2)P═NSiMe(3))(2))] (4), [Cp(2)U(C(Ph(2)P═NSiMe(3))(2))] (5), [TpTh(C(Ph(2)P═NSiMe(3))(2))Cl] (6), and [TpU(C(Ph(2)P═NSiMe(3))(2))Cl] (7) were generated from 2 or 3 by further reaction with 2 equiv of thallium(I) cyclopentadienide (CpTl) in THF to yield 4 or 5 or with 1 equiv of potassium hydrotris(pyrazol-1-yl) borate (TpK) also in THF to give 6 or 7, respectively. The derivative complexes were isolated, and their crystal structures were determined by X-ray diffraction. All of these U (or Th)-carbene complexes (4-7) possess a very short M (Th or U)═carbene bond with evidence for multiple bond character. Gaussian 03 DFT calculations indicate that the M═C double bond is constructed by interaction of the 5f and 6d orbitals of the actinide metal with carbene 2p orbitals of both π and σ character. Complex 3 reacted with acetonitrile or benzonitrile to cyclo-add C≡N to the U═carbon double bond, thereby forming a new C-C bond in a new chelated quadridentate ligand in the bridged dimetallic complexes (9 and 10). A single carbon-U bond is retained. The newly coordinated uranium complex dimerizes with one equivalent of unconverted 3 using two chlorides and the newly formed imine derived from the nitrile as three connecting bridges. In addition, a new crystal structure of [CpUCl(3)(THF)(2)] (8) was determined by X-ray diffraction.

A geminal dithallated bis(iminodiphenylphosphorano)methine carbon bridged dimer bound by Tl-Tl interactions.

A geminal dithallated bis(iminodiphenylphosphorano)methine carbon complex was prepared and isolated as a solid dimer, stable in an inert atmosphere. It has been fully characterized in both solution and solid states. Bonding has been assessed with the aid of DFT calculations. All data demonstrate that the dimer contains a single carbon center sigma bound to two Tl((I)) atoms (Tl((I))-C-Tl((I))). Two geminal monomers associate via Tl((I))-Tl((I)) interactions to form the dimer.

Solid-state 115In and 31P NMR studies of triarylphosphine indium trihalide adducts.

Solid-state (115)In and (31)P NMR spectroscopy, relativistic density functional theory (DFT) calculations, and single-crystal X-ray diffraction were used to investigate a series of triarylphosphine indium(III) trihalide adducts, X(3)In(PR(3)) and X(3)In(PR(3))(2) (X = Cl, Br or I; PR(3) = triarylphosphine ligand). The electric field gradient tensors at indium as well as the indium and phosphorus magnetic shielding tensors and the direct and indirect (115)In-(31)P spin-spin coupling were characterized; for complexes possessing a C(3) symmetry axis, the anisotropy in the indirect spin-spin coupling, DeltaJ((115)In,(31)P), was also determined. The (115)In quadrupolar coupling constants, C(Q)((115)In), range from +/-1.25 +/- 0.10 to -166.0 +/- 2.0 MHz. For any given phosphine ligand, the indium nuclei are most shielded for X = I and least shielded for X = Cl, a trend also observed for other group-13 nuclei in M(III) complexes. This experimental trend, attributed to spin-orbit effects of the halogen ligands, is reproduced by the DFT calculations. The spans of the indium magnetic shielding tensors for these complexes, delta(11)-delta(33), range from 40 +/- 7 to 710 +/- 60 ppm; those determined for phosphorus range from 28 +/- 1.5 to 50 +/- 3 ppm. Values of (1)J((115)In,(31)P) range from 550 +/- 20 to 2500 +/- 20 Hz. For any given halide, the (1)J((115)In,(31)P) values generally increase with increasing basicity of the PR(3) ligand. Calculated values of (1)J((115)In,(31)P) and DeltaJ((115)In,(31)P) duplicate experimental trends and indicate that both the Fermi-contact and spin-dipolar Fermi-contact mechanisms make important contributions to the (1)J((115)In,(31)P) tensors.

Solid-state (115)In NMR study of indium coordination complexes.

The feasibility of solid-state (115)In NMR studies is demonstrated by an examination of four different coordination complexes: indium(III) acetylacetonate, indium(III) tris(tropolonato), indium(III) triiodide bis(tris(4-methoxyphenyl)phosphine oxide) and indium(III) trichloride tris(2,4,6-trimethoxyphenyl)phosphine. The results provide information about the electric field gradients and magnetic shielding at the indium nuclei through the nuclear quadrupolar and chemical shift parameters, respectively. The C(Q) values in these four complexes range between 106.0 +/- 2.0 and 200.0 +/- 4.0 MHz, while the magnetic shielding anisotropies fall in the range from 85 +/- 15 to 550 +/- 60 ppm. Finally, this research demonstrates that solid-state (115)In NMR studies are facilitated by performing experiments at the highest possible magnetic-field strengths, and that NMR offers a promising tool for the characterization of indium compounds.

Modification of binuclear Pt-Tl bonded complexes by attaching bipyridine ligands to the thallium site.

Complex formation of monomeric thallium(III) species with 2,2'-bipyridine (bipy) in dimethyl sulfoxide (dmso) and acetonitrile solutions was studied by means of multinuclear ((1)H, (13)C, and (205)Tl) NMR spectroscopy. For the first time, NMR signals of the individual species [Tl(bipy)(m)(solv)](3+) (m = 1-3) were observed despite intensive ligand and solvent exchange processes. The tris(bipy) complex was crystallized as [Tl(bipy)(3)(dmso)](ClO(4))(3)(dmso)(2) (1), and its crystal structure determined. In this compound, thallium is seven-coordinated; it is bonded to six nitrogen atoms of the three bipy molecules and to an oxygen atom of dmso. Metal-metal bonded binuclear complexes [(NC)(5)Pt-Tl(CN)(n)(solv)](n)(-) (n = 0-3) have been modified by attaching bipy molecules to the thallium atom. A reaction between [(NC)(5)Pt-Tl(dmso)(4)](s) and 2,2'-bipyridine in dimethyl sulfoxide solution results in the formation of a new complex, [(NC)(5)Pt-Tl(bipy)(solv)]. The presence of a direct Pt-Tl bond in the complex is convincingly confirmed by a very strong one-bond (195)Pt-(205)Tl spin-spin coupling ((1)J((195)Pt-(205)Tl) = 64.9 kHz) detected in both (195)Pt and (205)Tl NMR spectra. In solutions containing free cyanide, coordination of CN(-) to the thallium atom occurs, and the complex [(NC)(5)Pt-Tl(bipy)(CN)(solv)](-) ((1)J((195)Pt-(205)Tl) = 50.1 kHz) is formed as well. Two metal-metal bonded compounds containing bipy as a ligand were crystallized and their structures determined by X-ray diffractometry: [(NC)(5)Pt-Tl(bipy)(dmso)(3)] (2) and [(NC)(5)Pt-Tl(bipy)(2)] (3). The Pt-Tl bonding distances in the compounds, 2.6187(7) and 2.6117(5) A, respectively, are among the shortest reported separations between these two metals. The corresponding force constants in the molecules, 1.38 and 1.68 N/cm, respectively, were calculated using Raman stretching frequencies of the Pt-Tl vibrations and are characteristic for a single metal-metal bond. Electronic absorption spectra were recorded for the [(NC)(5)Pt-Tl(bipy)(m)(solv)] compounds, and the optical transition was attributed to the metal-metal bond assigned.

The trigonal-bipyramidal triiodothallium(III) complex [TlI(3)[(CH(3))(2)SO]2].

The title compound, bis(dimethyl sulfoxide)triiodothallium(III), [TlI(3)(C(2)H(6)OS)(2)], was crystallized from equimolar amounts of Tl(I)I and I(2) in a dimethyl sulfoxide (DMSO) solution. After the initial redox reaction, the thallium(III)-iodo complex forms and precipitates as a DMSO solvate. In the crystal structure, Tl is surrounded by three iodide ligands in the equatorial plane and two O-coordinated DMSO molecules in the axial positions, forming a slightly distorted trigonal bipyramid. The complex lies on a twofold rotation axis, making the DMSO molecules and two of the I atoms crystallographically equivalent.