New approach to online monitoring of the Al depth profile of the hot-dip galvanised sheet steel using LIBS

In this study a new approach to the online monitoring of the Al depth profile of hot-dip galvanised sheet steel is presented, based on laser-induced breakdown spectroscopy (LIBS). The coating composition is measured by irradiating the traversing sheet steel with a series of single laser bursts, each at a different sheet steel position. An ablation depth in the same range as the coating thickness (about 10 μm) is achieved by applying a Nd:YAG laser at 1064 nm in collinear double-pulse and triple-pulse mode. The ablation depth is controlled by adjusting the burst energy with an external electro-optical attenuator. A fingerprint of the depth profile is gained by measuring the LIBS signals from zinc, aluminium and iron as a function of the burst energy, and by post-processing the data obtained. Up to three depths can be sampled simultaneously with a single laser burst by measuring the LIBS signals after each pulse within the laser burst. A concept for continuously monitoring the Al depth profile during the galvanising process is presented and applied to different hot-dip galvanised coatings. The method was tested on rotating sheet steel disks moving at a speed of up to 1 m/s. The potential and limitations of the new method are discussed.     

Parallel detection,quantification, and depth profiling of peptides with dynamic-secondary ion mass spectrometry (D-SIMS) ionized by C60–Ar co-sputtering

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) using pulsed C₆₀⁺ primary ions is a promising technique for analyzing biological specimens with high surface sensitivities. With molecular secondary ions of high masses, multiple molecules can be identified simultaneously without prior separation or isotope labeling. Previous reports using the C₆₀⁺ primary ion have been based on static-SIMS, which makes depth profiling complicated. Therefore, a dynamic-SIMS technique is reported here. Mixed peptides in the cryoprotectant trehalose were used as a model for evaluating the parameters that lead to the parallel detection and quantification of biomaterials. Trehalose was mixed separately with different concentrations of peptides. The peptide secondary ion intensities (normalized with respect to those of trehalose) were directly proportional to their concentration in the matrix (0.01–2.5 mol%). Quantification curves for each peptide were generated by plotting the percentage of peptides in trehalose versus the normalized SIMS intensities. Using these curves, the parallel detection, identification, and quantification of multiple peptides was achieved. Low energy Ar⁺ was used to co-sputter and ionize the peptide-doped trehalose sample to suppress the carbon deposition associated with C₆₀⁺ bombardment, which suppressed the ion intensities during the depth profiling. This co-sputtering technique yielded steadier molecular ion intensities than when using a single C₆₀⁺ beam. In other words, co-sputtering is suitable for the depth profiling of thick specimens. In addition, the smoother surface generated by co-sputtering yielded greater depth resolution than C₆₀⁺ sputtering. Furthermore, because C₆₀⁺ is responsible for generating the molecular ions, the dosage of the auxiliary Ar⁺ does not significantly affect the quantification curves.     

Depth profile analysis of various titanium based coatings on steel and tungsten carbide using laser ablation inductively coupled plasma –“time of flight” mass spectrometry

A homogenized 193 nm ArF* laser ablation system coupled to an inductively coupled plasma-”Time of Flight”-mass spectrometer (LA-ICP-TOFMS) was tested for depth profiling analysis on different single-layer Ti based coatings on steel and W carbides. Laser parameters, such as repetition rate, pulse energy and spatial resolution were tested to allow optimum depth related calibration curves. The ablation process using a laser repetition rate of 3 Hz, 120 μm crater diameter, and 100 mJ output energy, leads to linear calibration curves independent of the drill time or peak area used for calibrating the thickness of the layer. The best depth resolution obtained (without beam splitter) was 0.20 μm per laser shot. The time resolution of the ICP-TOFMS of 102 ms integration time per isotope was sufficient for the determination of the drill time of the laser through the coatings into the matrix with better than 2.6% RSD (about 7 μm coating thickness, n = 7). Variation of the volume of the ablation cell was not influencing the depth resolution, which suggests that the depth resolution is governed by the ablation process. However, the application on the Ti(N,C) based single layer shows the potential of LA-ICP-TOFMS as a complementary technique for fast depth determinations on various coatings in the low to medium μm region.     

Towards understanding monomer coordination in atom transfer radical polymerization: synthesis of [Cu(PMDETA)(π-M)][BPh4] (M = methyl acrylate, styrene, 1-octene, and methyl methacrylate) and structural studies by FT-IR and H NMR spectroscopy and X-ray crystallography

Cu^I complexes of the form [Cu^I(PMDETA)(π-M)][BPh₄] (where PMDETA = N,N,N′,N″,N″-pentamethyldiethylenetriamine, and M = vinyl monomer) were synthesized and isolated from solution as crystals with methyl acrylate (MA), styrene (Sty), and 1-octene (Oct). The interaction of the CC double bond of the vinyl monomer with Cu^I was characterized via FT-IR and ¹H NMR spectroscopy and single crystal X-ray crystallography. A fourth complex with methyl methacrylate (MMA) was synthesized and characterized spectroscopically, but no crystals suitable for X-ray structure analysis could be obtained. In all complexes, PMDETA acts as a tridentate ligand, while the pseudotetrahedral coordination geometry around Cu^I is completed by a π-interaction with the CC double bond of M in the presence of a non-coordinating counter-ion. A decrease in CC IR stretching frequencies of Δν(CC) = −110, −80, −109, and −127 cm⁻¹ for complexes with MA, Sty, Oct, and MMA, respectively, was observed upon coordination. No significant change in CC bond length was seen in the crystal structure for complexes with MA and Oct while a slight lengthening was observed for the Sty complex. The upfield shift of the vinyl proton resonances indicated the presence of significant π-back-bonding.     

Systematic line selection for online coating thickness measurements of galvanised sheet steel using LIBS

LIBS can be used as an online method of characterizing galvanized coatings on sheet steel moving through a production line. The traversing sheet steel is irradiated with a series of single laser bursts, each at a different position on the sheet steel. An ablation depth in the same range as the coating thickness (about 10 μm) is achieved by using a Nd:YAG laser at 1064 nm in collinear double-pulse mode. The coating thickness is determined from the ratio of the intensities of an iron line and a zinc line measured at a burst energy high enough to penetrate the coating with a single burst. Experiments at different burst energies were carried out to optimize the thickness resolution, and a method of systematically selecting iron and zinc lines was deduced, which is based on multivariate data analysis (MVDA) of the intensity ratios calculated for a set of 6 zinc lines and 21 iron lines. A temperature correction was applied, because the parameters of the plasma change with burst energy, and the influence of this on the thickness resolution is discussed. The ambient atmosphere present (air, Ar, N₂) as well as self-absorption of spectral lines both have an influence on the thickness resolution. At optimum conditions, a thickness measurement accuracy of better than 150 nm was obtained for a set of electrolytic galvanized sheet steels with coating thicknesses in the range 4.1–11.2 μm.     

The extended chain compounds Ln12(C2)3I17 (Ln=Pr, Nd, Gd, Dy): Synthesis, structure and physical properties

The title compounds are obtained in high yield from stoichiometric mixtures of Ln, LnI₃ and graphite, heated at 900-950 °C in welded Ta containers. The crystal structures of new Pr and Nd phases determined by single-crystal X-ray diffraction are related to those of other Ln₁₂(C₂)₃I₁₇-type compounds (C 2/c, a=19.610(1) and 19.574(4) Å, b=12.406(2) and 12.393(3) Å, c=19.062(5) and 19.003(5) Å, β=90.45(3)° and 90.41(3)°, for Pr₁₂(C₂)₃I₁₇ and Nd₁₂(C₂)₃I₁₇, respectively). All compounds contain infinite zigzag chains of C₂-centered metal atom octahedra condensed by edge-sharing into the [tcc]_∞ sequence (c=cis, t=trans) and surrounded by edge-bridging iodine atoms as well as by apical iodine atoms that bridge between chains. The polycrystalline Gd₁₂(C₂)₃I₁₇ sample exhibits semiconducting thermal behavior which is consistent with an ionic formulation (Ln³⁺)₁₂(C₂^6-)₃(I⁻)₁₇(e⁻) under the assumption that one extra electron is localized in metal-metal bonding. The magnetization measurements on Nd₁₂(C₂)₃I₁₇, Gd₁₂(C₂)₃I₁₇ and Dy₁₂(C₂)₃I₁₇ indicate the coexistence of competing magnetic interactions leading to spin freezing at T_f=5 K for the Gd phase. The Nd and Dy compounds order antiferromagnetically at T_N=25 and 29 K, respectively. For Dy₁₂(C₂)₃I₁₇, a metamagnetic transition is observed at a critical magnetic field H≈25 kOe.     

A comparative study of the effects of different buffer gases on the line shape of water vapour rovibronic transition

The line shape parameters of water vapour rovibrational transition at 12145.444 cm⁻¹ belonging to the (2ν₁ + ν₂ + ν₃) overtone band in the presence of three buffer gases He, N₂ and CO₂ are studied by high resolution near infrared (NIR) diode laser spectrometer. The wavelength modulation spectroscopy (WMS) is adopted to probe buffer gas broadened first derivative (1f) signal of water vapour transition. The simulation of the experimental signals based on Voigt profile provides the collisional broadening coefficients and line strength parameters. The comparison is made between the broadening effects on water vapour transition induced by He, N₂ and CO₂.     

Preparation,spectroscopic characterization and X-ray crystal and molecular structures of nickel(II), copper(II) and zinc(II) complexes of the Schiff base formed from isatin and S-methyldithiocarbazate (Hisa-sme)

Complexes of general formula, [M(isa-sme)₂] · n(solvate) [M = Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺; isa-sme = monoanionic form of the Schiff base formed by condensation of isatin with S-methyldithiocarbazate; n = 1 or 1.5; solvate = MeCN, DMSO, MeOH or H₂O] have been synthesized and characterized by a variety of physicochemical techniques. An X-ray crystallographic structure determination of the [Ni(isa-sme)₂] · MeCN complex reveals a six-coordinate, distorted octahedral geometry. The two uninegatively charged, tridentate, Schiff base ligands are coordinated to the nickel(II) ion meridionally via the amide O-atoms, the azomethine N-atoms and the thiolate S-atoms. By contrast, the crystal structure of [Zn(isa-sme)₂] · MeOH shows a four-coordinate distorted tetrahedral geometry. The two dithiocarbazate ligands are coordinated as N, S bidentate chelates with the amide O-atom not coordinated. The structure of the copper(II) complex [Cu(isa-sme)₂] · DMSO is complicated and comprises two different complexes in the asymmetric unit, one four- and the other five-coordinate. The four-coordinate copper(II) has a distorted (flattened) tetrahedral geometry as seen in the Zn(II) analogue whereas the five-coordinate copper(II) has a distorted square-pyramidal geometry with one ligand coordinated to the copper(II) ion as a tridentate (N, S, O) ligand and the other coordinated as a bidentate N, S chelate. EPR spectroscopy indicates that in solution only one form is present, that being a distorted tetrahedral complex.     

Depth profile analysis of various titanium based coatings on steel and tungsten carbide using laser ablation inductively coupled plasma--"time of flight" mass spectrometry

A homogenized 193 nm ArF* laser ablation system coupled to an inductively coupled plasma-"Time of Flight"-mass spectrometer (LA-ICP-TOFMS) was tested for depth profiling analysis on different single-layer Ti based coatings on steel and W carbides. Laser parameters, such as repetition rate, pulse energy and spatial resolution were tested to allow optimum depth related calibration curves. The ablation process using a laser repetition rate of 3 Hz, 120 microm crater diameter, and 100 mJ output energy, leads to linear calibration curves independent of the drill time or peak area used for calibrating the thickness of the layer. The best depth resolution obtained (without beam splitter) was 0.20 microm per laser shot. The time resolution of the ICP-TOFMS of 102 ms integration time per isotope was sufficient for the determination of the drill time of the laser through the coatings into the matrix with better than 2.6% RSD (about 7 microm coating thickness, n = 7). Variation of the volume of the ablation cell was not influencing the depth resolution, which suggests that the depth resolution is governed by the ablation process. However, the application on the Ti(N,C) based single layer shows the potential of LA-ICP-TOFMS as a complementary technique for fast depth determinations on various coatings in the low to medium microm region.     

Buffer gas effect on monitoring I2 by a laser induced fluorescence method

Based on the measured N₂ pressure dependence of high resolution fluorescence excitation spectra for ¹²⁷I₂ near the He-Ne laser frequency, effects of the N₂ pressure on the I₂ detection limit and isotopic selectivity of an on-line I₂ monitor using a laser induced fluorescence method are discussed. A possible influence from NO₂, which is contained in reprocessing off-gas streams, on monitoring I₂ is also examined. The ¹²⁷I₂ in N₂ at atmospheric pressure is detected down to a concentration of 5 × 10¹² molecules cm⁻³ by a ³He-²⁰Ne laser induced fluorescence method.     

Effects of the temperature and beam parameters on depth profiles in X-ray photoelectron spectrometry and secondary ion mass spectrometry under C60–Ar cosputtering

Polymethylmethacrylate (PMMA) is widely used in various fields, including the semiconductor, biomaterial and microelectronic fields. Obtaining the correct depth profiles of PMMA is essential, especially when it is used as a thin-film. There have been many studies that have used earlier generation of cluster ion (SF₅⁺) as the sputtering source to profile PMMA films, but few reports have discussed the use of the more recently developed C₆₀⁺ in the PMMA sputtering process. In this study, X-ray photoelectron spectroscopy (XPS) and dynamic secondary ion mass spectroscopy (D-SIMS) were used concurrently to monitor the depth profiles of PMMA under C₆₀⁺ bombardment. Additionally, the cosputtering technique (C₆₀⁺ sputtering with auxiliary, low-kinetic-energy Ar⁺) was introduced to improve the analytical results. The proper cosputtering conditions could eliminate the signal enhancement near the interface that occurred with C₆₀⁺ sputtering and enhance the sputtering yield of the characteristic signals. Atomic force microscopy (AFM) was also used to measure the ion-induced topography. Furthermore, the effect of the specimen temperature on the PMMA depth profile was also examined. At higher temperatures (+120 °C), the depolymerization reaction that corresponded to main-chain scission dominated the sputtering process. At lower temperatures (−120 °C), the cross-linking mechanism was retarded significantly due to the immobilization of free radicals. Both the higher and lower sample temperatures were found to further improve the resulting depth profiles.     

Influence of the surface structure on the initiation of nuclear-chemical processes under laser ablation of metals in aqueous media

It is shown that the efficiency of nucleochemical transformations under conditions of laser ablation of metals in aqueous media under the influence of picosecond laser pulses with peak intensity I _E ～ 10¹⁰–10¹³ W/cm² is largely determined by features of the metal’s surface relief in the region of high spatial frequencies (nanometer range) formed under these conditions. This is found through an atomic force microscopy study of the relief features of such surfaces formed with different laser ablation modes on specially prepared model samples. Analysis of the obtained images by means of flicker-noise spectroscopy with key 3D surface parameters in the nanometer range allow us to associate the rates of nuclear processes initiated upon laser ablation with sharpness factor as a measure of the chaotic constituent of the relief profile of a forming surface at the highest spatial frequencies. It is found that it is in the neighborhood of the greatest high-frequency irregularities of the surface that electric fields with the highest voltage that lowers the energy barrier to electron injection from the metal (the Frenkel effect) are located and the elevated values of mechanical tensile stresses that also contribute to reducing the work of an electron escaping from the metal (the Zhurkov effect) are found. It is concluded that the sharpness factor must play the key role in raising kinetic energy of electrons E _e to ～5–10 eV in the subsurface regions of low-temperature plasma formed upon laser ablation in the metal subsurface region in which the above nucleochemical transformations can occur.     

Syntheses and evaluation of 7-deoxycholic amide-based tweezer-type copper(II) ion-selective ionophores

Seven tweezer-type copper(II) ion-selective ionophores; that is, 3α,12α-bis[[[N-(R)thiocarboxamino]acetyl]oxy]-N,N-dioctyl-5β-cholan-24-amides and 3α,12α-bis[[[N-(R)thiocarboxaminomethyl]acetyl]oxy]-N,N-dioctyl-5β-cholan-24-amides (R = alkyl and phenyl), were newly designed and synthesized. Their potentiometric evaluation of the poly(vinyl chloride) (PVC) membranes showed excellent affinity and selectivity to copper(II) ions over those of other transition metal ions and alkali/alkaline earth metal ions. These membranes exhibited super-Nernstian responses toward copper(II) ions (34-36 mV/decade), with detection limits of 10⁻⁶-10⁻⁷ M.     

Direct Determination of Copper in Solids and Ores by Laser Ablation-Direct Current Argon Plasma Emission Spectrometry

Abstract

The use of a laser ablation-direct current argon plasma emission spectrometric system for the direct determination of metals in solids is described. Sample preparation of solid steel samples involves machining to fit the geometry of the ablation chamber. A cellulose binder and copper ore are mixed thoroughly in a ball mill to ensure homogeneity and pelletized in a press at 20000 psi to fit the geometry of the ablation chamber. Copper, manganese, and nickel are determined using the system on standard steel samples, and copper is determined in pelletized copper ore with good agreement obtained with certified values. Precisions are typically in the 3 - 10% range with a detectable limit of 100 μg g^?1 of copper.     

Depth profile studies of ZrTiN coatings by laser ablation inductively coupled plasma mass spectrometry

The feasibility of depth profiling was studied by using a 193-nm ArF* excimer laser ablation system (GeoLas, MicroLas, Goettingen, Germany) with a lens array-based beam homogenizer in combination with an ICP-QMS Agilent 7500. Two ablation cells (20 and 1.5 cm³) were compared at the laser repetition rate of 1 Hz, laser beam energy of 135 mJ and the carrier gas flow rate 1.5 L min^–1 He + 0.78 L min^–1 Ar. The ablation cell dimensions are important parameters for signal tailing; however, very small cell volumes (e.g. 1.5 cm³) may cause memory effects, which can be probably explained by dominant inertial losses of aerosol on cell walls with its delayed mobilization. The 20-cm³ ablation cell seems to be appropriate for depth profiling by continuous single-hole drilling. The study of the influence of the pit diameter magnitude on the waning and emerging signals under small crater depth/diameter aspect ratios, which range between 0.75 and 0.0375 for the 3-m-thick coatings and pit diameters 4–80 m, revealed that the steady-state signals of pure coating and pure substrate (out of interface) were obtained at crater diameters between 20 and 40 m. Depth resolution defined by means of slopes of tangents in the layer interface region depend on the pit diameter and has an optimum value between 20 and 40 m and gives 0.6 m for the 20-m pit. In-depth variation of concentration of coating constituent (Ti) was proved to be almost identical with two different laser/ICP systems.Viktor Kanický performed this work while on leave at ETH Zurich     

Synthesis, characterization, photophysical and electrochemical properties of new phosphorescent dopants for OLEDs

New heteroleptic iridium(III) complexes of 2-(p-substituted-phenyl)-pyridine were synthesized and characterized. These complexes have two cyclometalated ligands (C^∧N) and a bidentate ancillary ligand (LX), that is, (C^∧N)₂Ir(LX). LX was either acetylacetonate or 5-nitro-8-hydroxy quinolate. Substitution on the p-phenyl of C^∧N ligands was used to alter the electronic properties of these complexes. The (C^∧N)₂Ir(acac) complexes show phosphorescence with good quantum yields and microsecond lifetimes and also show photoluminescence over a wide visible range (λ_max = 503-620 nm). The HOMO level and triplet energy level of these complexes were also determined. These data indicate their potential use as emitting materials for organic light emitting diodes, OLEDs.     

Synthesis, characterization, and norbornene polymerization of η-benzylnickel(II) complexes of N-heterocyclic carbenes

Neutral η¹-benzylnickel carbene complexes, [Ni(η¹-CH₂C₆H₅)(IiPr)(PMe₃)(Cl)] (3) (IiPr = 1,3-bis-(2,6-diisopropylphenyl)imidazol-2-ylidene) and [Ni(η¹-CH₂C₆H₅)(SIiPr)(PMe₃)(Cl)] (4) (SIiPr = 1,3-bis-(2,6-diisopropylphenyl)imidazolin-2-ylidene), were prepared by the reaction between [Ni(η³-CH₂C₆H₅)(PMe₃)(Cl)] and an equivalent amount of the corresponding free N-heterocyclic carbene. The preparation of η³-benzylnickel carbene complexes, [Ni(η³-CH₂C₆H₅)(IiPr)(Cl)] (5) and [Ni(η³-CH₂C₆H₅)(SIiPr)(Cl)] (6) were carried out by the abstraction of PMe₃ from 3 and 4 by the treatment of B(C₆F₅)₃. The treatment of AgX on 5 and 6 produced the anion-exchanged complexes, [Ni(η³-CH₂C₆H₅)(NHC)(X)] (7, NHC = IiPr, X = O₂CCF₃; 8, NHC = IiPr, X = O₃SCF₃; 9, NHC = SIiPr, X = O₂CCF₃; 10, NHC = SIiPr, X = O₃SCF₃). The solid state structures of 3 and 10 were determined by X-ray crystallography. The η³-benzyl complexes of IiPr (5, 7, and 8) alone, in the absence of any activators such as borate and MAO, showed good catalytic activity towards the vinyl-type norbornene polymerization. The catalyst was thermally robust and the activity increases as the temperature rises to 130 °C.     

Synthesis,characterization and crystal structures of the bidentate Schiff base N,N′‐bis(2‐nitrocinnamaldehyde)ethylenediamine and its complex with CuNCS and triphenylphosphane

Reaction of copper(I) thiocyanate and triphenylphosphane with the bidentate Schiff base N,N′‐bis(trans‐2‐nitrocinnamaldehyde)ethylenediamine {Nca₂en, (1); systematic name (1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]}, C₂₀H₁₈N₄O₄, in a 1:1:1 molar ratio in acetonitrile resulted in the formation of the complex {(1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]‐κ²N,N′}(thiocyanato‐κN)(triphenylphosphane‐κP)copper(I)], [Cu(NCS)(C₂₀H₁₈N₄O₄)(C₁₈H₁₅P)] or [Cu(NCS)(Nca₂en)(PPh₃)], (2). The Schiff base and copper(I) complex have been characterized by elemental analyses, IR, electronic and ¹H NMR spectroscopy, and X‐ray crystallography [from synchrotron data for (1)]. The molecule of (1) lies on a crystallographic inversion centre, with a trans conformation for the ethylenediamine unit, and displays significant twists from coplanarity of its nitro group, aromatic ring, conjugated chain and especially ethylenediamine segments. It acts as a bidentate ligand coordinating via the imine N atoms to the Cu^I atom in complex (2), in which the ethylenediamine unit necessarily adopts a somewhat flattened gauche conformation, resulting in a rather bowed shape overall for the ligand. The NCS⁻ ligand is coordinated through its N atom. The geometry around the Cu^I atom is distorted tetrahedral, with a small N—Cu—N bite angle of 81.56 (12)° and an enlarged opposite angle of 117.29 (9)° for SCN—Cu—P. Comparisons are made with the analogous Schiff base having no nitro substituents and with metal complexes of both ligands.     

Application of laser ablation inductively coupled plasma mass spectrometry for the isotopic analysis of single uranium particles

The paper describes the application of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for the isotopic analysis of individual uranium-oxide particles. The procedure developed is suitable for the accurate measurement of ²³⁴U, ²³⁵U, ²³⁶U and ²³⁸U isotopes in single actinide particles with lateral dimensions down to 10 μm. The ²³⁵U/²³⁸U isotope ratios can be obtained with a precision of a few percent relative standard deviation using a single collector ICP-MS instrument. The precision could be improved by the use of slow ablation and by taking several LA-ICP-MS replicate spectra on the same particle investigated. For the minor isotopes use of higher mass resolution (R = 4000) was necessary in some cases to avoid spectral interferences. The technique developed offers a rapid and accurate possibility for the isotopic composition determination of uranium-containing individual particles in environmental and safeguards samples.     

Structural features of tricarbonyl(N-methyl-2-pyridinecarboxyamide)chloro-rhenium(I)-potential precursor of radiopharmaceuticals

Structural characteristics of the novel [fac-Re(CO)₃L]Cl complex, where L denotes the N-methyl-2-pyridinecarboxyamide, are presented. Molecular structure of the complex has been established by means of X-ray single crystal diffraction and compared with quantum mechanical calculations. It has been shown that pyridinethioamide is softer base than pyridineamide. As a result of different Re^I–S and Re^I–O bond covalent shortenings (reflecting their diverse ionic/covalent character ratio) difference of the bond lengths decreases from a theoretical value of 0.45 Å to the value of 0.28 Å.