Excited-state absorption properties of platinum(II) terpyridyl acetylides

A comprehensive photophysical study is presented which compares the ground- and excited-state properties of four platinum(II) terpyridyl acetylide compounds of the general formula [Pt(tBu3tpy)(CCR)]+, where tBu3tpy is 4,4',4' '-tri-tert-butyl-2,2':6',2' '-terpyridine and R is an alkyl or aryl group. [Ru(tBu3tpy)3]2+ and the pivotal synthetic precursor [Pt(tBu3tpy)Cl]+ were also investigated in the current work. The latter two complexes possess short excited-state lifetimes and were investigated using ultrafast spectrometry while the other four compounds were evaluated using conventional nanosecond transient-absorption spectroscopy. The original intention of this study was to comprehend the nature of the impressive excited-state absorptions that emanate from this class of transition-metal chromophores. Transient-absorbance-difference spectra across the series contain the same salient features, which are modulated only slightly in wavelength and markedly in intensity as a function of the appended acetylide ligand. More intense absorption transients are observed in the arylacetylide structures relative to those bearing an alkylacetylide, consistent with transitions coupled to the pi system of the ancillary ligand. Reductive spectroelectrochemical measurements successfully generated the electronic spectrum of the tBu3tpy radical anion in all six complexes at room temperature. These measurements confirm that electronic absorptions associated with the tBu3tpy radical anion simply do not account for the intense optical transitions observed in the excited state of the Pt(II) chromophores. Transient-trapping experiments using the spectroscopically silent reductive quencher DABCO clearly demonstrate the loss of most transient-absorption features in the acetylide complexes throughout the UV, visible, and near-IR regions following bimolecular excited-state electron transfer, suggesting that these features are strongly tied to the photogenerated hole which is delocalized across the Pt center and the ancillary acetylide ligand.     

Monocarbonyl cationic rhodium(I) complexes

Summary The preparations and characterisation of cationic complexes of the type [Rh(CO)(MeCN)(PR₃)₂]ClO₄, [Rh(CO)L(PR₃)₂]ClO₄ (L=py or 2-MeOpy), [Rh(CO)(L-L)(PR₃)₂]ClO₄ (L-L = bipy or phen) and [Rh(CO)(PR₃)₃]ClO₄ with PR₃ = P(p-YC₆H₄)₃ (Y=Cl, F, Me or MeO) are described.     

Free-radical reactions of diazonium salts with α,β-unsaturated carbonyl compounds. A new synthesis of 1,4-diarylpyrazole derivatives

Free-radical decomposition of diazonium salts catalyzed by titanous or titanous and ferrous salts in the presence of β-substituted α,β-unsaturated carbonyl compounds leads to 1,4-diarylpyrazole derivatives. The reaction occurs via an intermediate azo compound ( 1 ), which can be reduced by the metal salt or can be isolated and hydrogenated to pyrazole derivatives.     

σ‐Alkylpalladium Intermediates in Intramolecular Heck Reactions:Isolation and Catalytic Activity

The isolation of σ‐alkylpalladium Heck intermediates, possible when β‐hydride elimination is inhibited, is a rather rare event. Performing intramolecular Heck reactions on N‐allyl‐2‐halobenzylamines in the presence of [Pd(PPh₃)₄], we isolated and characterized a series of stable bridged palladacycles containing an iodine or bromine atom on the palladium atom. Indolyl substrates were also tested for isolation of the corresponding complexes. X‐ray crystallographic analysis of one of the indolyl derivatives revealed the presence of a five‐membered palladacycle with the metal center bearing a PPh₃ ligand and an iodine atom in a cis position with respect to the nitrogen atom. The stability of the σ‐alkylpalladium complexes is probably a consequence of the strong constraint resulting from the bridged junction that hampers the cisoid conformation essential for β‐hydride elimination. Subsequently, the thus obtained bridged five‐membered palladacycles were proven to be effective precatalysts in Heck reactions as well as in cross‐coupling processes such as Suzuki and Stille reactions.     

Synthesis and temperature dependence of physical properties of four pyridinium-based ionic liquids: Influence of the size of the cation

In this paper, the ionic liquids 1,2-diethylpyridinium ethylsulfate, EEpyESO₄; 1-methylpyridinium methylsulfate, MpyMSO₄; 1,3-dimethylpyridinium methylsulfate, MMpyMSO₄; and 2-ethyl-1-methylpyridinium methylsulfate, EMpyMSO₄; were synthesized in our laboratory, and their experimental densities, speeds of sound, dynamic viscosities, and refractive indices were studied as a function of temperature at atmospheric pressure. Thermal expansion coefficient, molar volume, and molar refraction of these ionic liquids were calculated from the experimental density and refractive index values.     

A crystalline sponge based on dispersive forces suitable for X-ray structure determination of included molecular guests

A crystalline porous material showing one-dimensional (1-D) rectangular micropores (12 × 9 Ų) has been assembled from a semirigid macrocyclic tetraimine and EtOAc as the templating agent. The 1-D nature of the material is intrinsic to the conformationally rigid structure of a macrocyclic sub-unit bearing four cyclohexylidene residues. The multiple dispersive forces established among the aliphatic residues glutted the 1-D channels and provided thermal stability to the material at temperatures below 160 °C. Upon removal of the template, the structure of the empty solid exhibited permanent microporosity (S _BET = 342 m² g^–1). Being a true molecular sponge, the channel framework of this material allowed the inclusion of a variety of molecular sample guests without compromising its crystalline nature. Remarkably, this crystalline material enabled the structure determination by X-ray diffraction of the included molecules. Theoretical studies demonstrated the vital role played by the dispersive forces in the overall stabilization of the crystal packing.     

The preparation,crystal structure and electrochemistry of (5Z,5′Z)-2,2′-(alkane-α,ω-diylsulfanyldiyl)bis(5-(3-pyridylmethylene)-3,5-dihydro-4H-imidazol-4-ones) and their complexes with cobalt(II) chloride

A series of S-alkylated derivatives of 2-thiohydantoins, containing two 5-(3-pyridylmethylene)-3,5-dihydro-4H-imiazole-4-one fragments joined by polymethylene bridges with different numbers of carbon atoms, was synthesized. The title (5Z,5′Z)-2,2′-(alkane-α,ω-diylsulfanyldiyl)bis(5-(3-pyridylmethylene)-3,5-dihydro-4H-imidazol-4-ones) (L) were obtained by alkylation of 5-(3-pyridylmethylene)-3-phenyl-2-thiohydantoine by 1,2-dibromoethane, 1,6-dibromohexane or 1,10-dibromodecane in DMF in the presence of potassium carbonate. The complexes of ligands L with CoCl₂ · 6H₂O have been synthesized. It is shown that, regardless of the L:CoCl₂ ratio, complexes with LCoCl₂ composition are obtained in all cases. The structure of the cobalt(II) chloride complex with (5Z,5′Z)-2,2′-(ethane-1,2-diyldisulfanyldiyl)bis(5-(3-pyridylmethylene)-3-phenyl-3,5-dihydro-4H-imidazol-4-one) was determined by means of the RSA method. The cobalt atom in this complex has a tetrahedral ligand environment and it is coordinated by two chloride anions and two nitrogen atoms of pyridine fragments, forming a 19-membered metallocycle. Electrochemical investigations of the synthesized ligands and complexes have been made by CVA and RDE methods. It is established that the first stage of reduction for the complexes takes place on the metal, whereas the first stage of oxidation takes place on the coordinated chloride-anions.     

Direct Bioelectrocatalysis by NADP‐Reducing Hydrogenase from Pyrococcus furiosus

The direct bioelectrocatalysis by an NAD(P)‐reducing hydrogenase is reported for the first time. In contrast to previous attempts to involve similar enzymes in bioelectrocatalysis [1–4], which were in fact unsuccessful, in our report an effective electrocatalysis by Pyrococcus furiosus hydrogenase is convincingly shown by (i) achievement of the hydrogen equilibrium potential and (ii) a high current of hydrogen oxidation (0.3 mA cm^?2 at 100 mV overpotential and at 75 °C). The latter is just a few times lower compared to enzyme electrodes based on NAD(P)‐independent hydrogenases.     

Dimerization mechanism of bis(triphenylphosphine)copper(I) tetrahydroborate: proton transfer via a dihydrogen bond

The mechanism of transition-metal tetrahydroborate dimerization was established for the first time on the example of (Ph(3)P)(2)Cu(η(2)-BH(4)) interaction with different proton donors [MeOH, CH(2)FCH(2)OH, CF(3)CH(2)OH, (CF(3))(2)CHOH, (CF(3))(3)CHOH, p-NO(2)C(6)H(4)OH, p-NO(2)C(6)H(4)N═NC(6)H(4)OH, p-NO(2)C(6)H(4)NH(2)] using the combination of experimental (IR, 190-300 K) and quantum-chemical (DFT/M06) methods. The formation of dihydrogen-bonded complexes as the first reaction step was established experimentally. Their structural, electronic, energetic, and spectroscopic features were thoroughly analyzed by means of quantum-chemical calculations. Bifurcate complexes involving both bridging and terminal hydride hydrogen atoms become thermodynamically preferred for strong proton donors. Their formation was found to be a prerequisite for the subsequent proton transfer and dimerization to occur. Reaction kinetics was studied at variable temperature, showing that proton transfer is the rate-determining step. This result is in agreement with the computed potential energy profile of (Ph(3)P)(2)Cu(η(2)-BH(4)) dimerization, yielding [{(Ph(3)P)(2)Cu}(2)(μ,η(4)-BH(4))](+).     

Mercury determination in urine samples by gold nanostructured screen-printed carbon electrodes after vortex-assisted ionic liquid dispersive liquid–liquid microextraction

A novel approach is presented to determine mercury in urine samples, employing vortex-assisted ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction to prepare samples, and screen-printed electrodes modified with gold nanoparticles for voltammetric analysis. Mercury was extracted directly from non-digested urine samples in a water-immiscible ionic liquid, being back-extracted into an acidic aqueous solution. Subsequently, it was determined using gold nanoparticle-modified screen-printed electrodes. Under optimized microextraction conditions, standard addition calibration was applied to urine samples containing 5, 10 and 15 μg L⁻¹ of mercury. Standard addition calibration curves using standards between 0 and 20 μg L⁻¹ gave a high level of linearity with correlation coefficients ranging from 0.990 to 0.999 (N = 5). The limit of detection was empirical and statistically evaluated, obtaining values that ranged from 0.5 to 1.5 μg L⁻¹, and from 1.1 to 1.3 μg L⁻¹, respectively, which are significantly lower than the threshold level established by the World Health Organization for normal mercury content in urine (i.e., 10–20 μg L⁻¹). A certified reference material (REC-8848/Level II) was analyzed to assess method accuracy finding 87% and 3 μg L⁻¹ as the recovery (trueness) and standard deviation values, respectively. Finally, the method was used to analyze spiked urine samples, obtaining good agreement between spiked and found concentrations (recovery ranged from 97 to 100%).