Investigation of charge transfer and structural distortions during photo-inducted excitation of cuprous bis-2,9-dimethyl-1,10-phenanthroline complex by density functional theory

This work reported the investigation of the structural distortions and charge-transfer processes that occurred in the complex of cuprous(I) bis-2,9-dimethyl-1,10-phenanthroline upon oxidation to copper(II), , through a excited state of by density functional theory. The intramolecular electronic transfer from central metal-to-ligand (MLCT) upon the irradiation of light energy is confirmed. Due to this MLCT excitation, the structure of the excited state of is distorted and reorganized to adapt with the change of charge in central metal. As a result, the excited state of is formed, which has the similar electronic and structural properties with . The bulky substituents in 2- and 9-positions of the phenanthroline ligands can restrain the structural distort and decrease nonradiative decay rate. Thus, the electronic and steric effects of the ligands in the cuprous photo-sensitive complexes have important consequences in the behavior of their excited state.     

Pyridinium amide-based simple synthetic receptor for selective recognition of dihydrogenphosphate

A new fluorescent receptor 1 built on biphenyl motif has been designed and synthesized. Pyridinium amide moiety in 1 acts as binding site and shows selective complexation of isophthalate and under the mastery of biphenyl spacer. Binding-induced increase in emission was used to determine the selectivity and sensitivity of 1 toward a series of anions such as different dicarboxylates, , , and . The binding characteristics were established by ¹H NMR, UV-vis, and fluorescence spectroscopic methods.     

Tetragonal low-temperature structure of LiAl

The cubic face-centered structure of LiAl (, at ) transforms into a tetragonal body-centered structure (I4₁/amd, , at ). This first-order phase transition at about during heating is probably the reason for the so-called “ anomalies” in some physical properties like specific heat, electrical resistivity and nuclear-spin lattice relaxation. This transition seems to be correlated with the composition Li:Al of the alloy and the amount of Li vacancies.     

The partial molar heat capacity, expansion, isentropic, and isothermal compressions of thymidine in aqueous solution at T = 298.15 K

Solution densities have been determined for aqueous solutions of thymidine at T = (288.15, 298.15, 303.15, and 313.15) K. The partial molar volumes at infinite dilution, , obtained from the density data were used to derive the partial molar isobaric expansion at infinite dilution for thymidine at T = 298.15 K, . The partial molar heat capacity at infinite dilution for thymidine, , at T = 298.15 K has also been determined. Sound speeds have been measured for aqueous solutions of thymidine at T = 298.15 K. The partial molar isentropic compression at infinite dilution, , and the partial molar isothermal compression at infinite dilution, , have been derived from the sound speed data. The , , , and results for thymidine are critically compared with those available from the literature.     

Synthesis and crystal structure of the isotypic rare earth thioborates Ce[BS3], Pr[BS3], and Nd[BS3]

The orthothioborates Ce[BS₃], Pr[BS₃] and Nd[BS₃] were prepared from mixtures of the rare earth (RE) metals together with amorphous boron and sulfur summing up to the compositions CeB₃S₆, PrB₅S₉ and NdB₃S₆. The following preparation routes were used: solid state reactions with maximum temperatures of 1323 K and high-pressure high-temperature syntheses at 1173 K and 3 GPa. Pr[BS₃] and Nd[BS₃] were also obtained from rare earth chlorides RECl₃ and sodium thioborate Na₂B₂S₅ by metathesis type reactions at maximum temperatures of 1073 K. The crystal structure of the title compounds was determined from X-ray powder diffraction data. The thioborates are isotypic and crystallize in the orthorhombic spacegroup Pna2₁ (No. 33; Z=4; Ce: , , ; Pr: , , ; Nd: , , ) . The crystal structures contain isolated [BS₃]^3‐ groups with boron in trigonal-planar coordination. The sulfur atoms form the vertices of undulated kagome nets, which are stacked along [100] according to the sequence ABAB. Within these nets every second triangle is occupied by boron and the large hexagons are centered by rare earth ions, which are surrounded by overall nine sulfur species.     

Ruthenium (II) complexes of the chelating phosphine borane H2ClB · dppm

Reaction of H₂ClB · PPh₂CH₂PPh₂ (H₂ClB · dppm) with results in displacement of all three acetonitrile ligands and the formation of (1), which has been characterised crystallographically. Reaction with carbon monoxide results in a change from η² to η¹ of the borane ligand to afford (2). Compound 1 undergoes H/D exchange under a D₂ atmosphere to afford , while 2 does not.     

Oxidative addition to main group versus transition metals: Insights from the Activation Strain model

We have studied the oxidative addition of the methane C-H and chloromethane C-Cl bonds to a number of main group (Be, Mg and Ca) and transition metals (Pd, Zn and Cd), using relativistic density functional theory (DFT) at ZORA-BLYP/TZ2P. The purpose is to better understand what causes the characteristic differences in reactivity between main group and transition metals towards oxidative addition. Thus, we have analyzed our model reactions using the Activation Strain model in which the activation energy ΔE^≠ is decomposed into the activation strain of and the stabilizing TS interaction between the reactants in the activated complex: . Activation of the C-H bond goes with higher barriers than activation of the C-Cl bond because the higher bond strength of the former translates into a higher activation strain . The barriers for bond activation increase along Pd < Be, Ca < Mg < Zn, Cd. This can be straightforwardly understood through the TS-interaction , that is, in terms of the bonding capabilities of the metals. Pd yields the lowest barriers because it achieves the most stabilizing . This is the result of the small HOMO-LUMO gap between its occupied 4d and unfilled 5s AOs, which makes Pd both a good electron donor and acceptor. Zn and Cd yield the highest barriers because the large HOMO-LUMO gap between the occupied valence ns and unfilled valence np AOs makes them both poor donors and poor acceptors of electronic charge.     

Adsorption of antimony(III) and antimony(V) on bentonite: Kinetics, thermodynamics and anion competition

This research attempted to study the adsorption of Sb(III) and Sb(V) on bentonite using batch experiments. The effects of reaction time, temperature, initial Sb concentration, and competitive anions at different concentrations on the adsorption of Sb(III) and Sb(V) were investigated. Kinetic studies suggested that the adsorption equilibriums for both Sb(III) and Sb(V) were reached within 24 h. The desorption of Sb adsorbate on the bentonite was observed following Sb(III) adsorption, probably due to the oxidation of Sb(III) on the bentonite surface and subsequent desorption of Sb(V). In addition, oxidation of Sb(III) can occur in the solution medium also, which decreases the concentration of Sb(III) in the solution thereby driving the equilibrium in the direction of desorption from the surface. The adsorption data at three temperatures were successfully modeled using Langmuir (r² > 0.82) and Freundlich (r² > 0.99) isotherms. The thermodynamic parameters (ΔG⁰, ΔH⁰, and ΔS⁰) were calculated from the temperature dependence, suggesting that the adsorption process of Sb(III) is spontaneously exothermic, while the adsorption process of Sb(V) is spontaneously endothermic. Competitive anions such as , , and hardly affected the Sb(III) adsorption on bentonite, while and could compete with for adsorption sites. The competition between and on adsorption sites was presumably due to the formation of surface complexes and the surface accumulation or precipitation of on bentonite surface.     

Monitoring structural transformations in crystals. Part 4. Monitoring structural changes in crystals of pyridine analogs of chalcone during [2+2]-photodimerization and possibilities of the reaction in hydroxy derivatives

We studied the [2+2]-photodimerization in crystals of pyridine analogs and hydroxy derivatives of chalcone using the X-ray structure analysis. The mutual orientation of adjacent molecules in the crystals was analyzed in a quantitative way and the results were compared with data for known photoactive crystals undergoing the [2+2]-photodimerization. In the case of one pyridine analog, we processed the single-crystal-to-single-crystal photodimerization and determined the structure for the mixed crystal containing both the substrate and the product. We also explained a role of hydrogen bonds in the [2+2]-photodimerization in the case of the hydroxy derivatives of chalcone. C₅H₄N-CO-CHCH-C₆H₅: , , , β=91.318(10)°, monoclinic, . The irradiated crystal of the above analog: , , , β=91.870(10)°, monoclinic, . C₆H₅-CO-CHCH-C₅H₄N: , , , β=110.01(3)°, monoclinic, C2/c,Z=8. C₆H₅-CO-CHCH-C₆H₄(o-OH): , , , β=109.73(5)°, monoclinic, . C₆H₅-CO-CHCH-C₆H₄(p-OH): , , , orthorhombic, .     

Syntheses of [F]5-fluoro-3-nitro-l-tyrosine

The detection of 3-nitro-l-tyrosine has been used as a biomarker of “reactive nitrogen species” in biological matrices and has been an ongoing challenge in analytical chemistry. In this work, fluorine-18 labelled 5-fluoro-3-nitro-l-tyrosine (FNT) was synthesized as a potential radiotracer to probe the biological fate of 3-nitro-l-tyrosine. The synthesis of []FNT was carried out by reaction of []3-fluoro-l-tyrosine with NaNO₃ in TFA solvent for 5 min at 4 °C. The radiochemical yield (RCY) of []FNT was 96±2% and []3-fluoro-l-tyrosine, was 29±1%, relative to []3-fluoro-l-tyrosine and []F₂, respectively. The syntheses of []FNT were also accomplished by direct fluorination of 3-nitro-l-tyrosine with []F₂ and by nitration of l-tyrosine with NaNO₃, followed by fluorination, in TFA (4 °C) or anhydrous HF (−65 °C) solvent. The latter two synthetic routes produced []FNT in 13.5±1.5% RCY, within 1 h. Products were characterized by use of , and NMR spectroscopy and mass spectrometry.     

Temperature-dependent diffraction studies on the phase evolution of tetraindium heptabromide

The mixed-valent compound In₄Br₇ undergoes a higher-order phase transition below which leads to a decrease in symmetry from the trigonal to the monoclinic (C2/c) system via . The phase transition has been monitored by X-ray powder diffraction using a linear position-sensitive detector between 15 and , and the crystal structures at room temperature and at 90 K have been refined by means of time-of-flight neutron powder-diffraction data; at , the lattice parameters are , , , and β=98.20(1)°; the new unit cell contains 88 atoms (Z=8) of which 12 are symmetry-independent. Due to their electronic instability because of a second-order Jahn-Teller effect, two of the three crystallographically independent monovalent indium cations are severely affected by the phase transition with respect to their coordination spheres; bond-valence calculations reveal significant strengthening of In⁺-Br⁻ bonding upon symmetry reduction. Structural changes and group-subgroup relationships as well as possible intermediate phases are discussed.     

Effect of initial monomer concentration on the equilibrium swelling and elasticity of hydrogels

The linear swelling ratio α and the effective network chain length N of a series of poly(N,N-dimethylacrylamide) (PDMAAm) hydrogels were investigated as a function of the gel preparation concentration . PDMAAm hydrogels were prepared at a fixed cross-linker ratio but at various initial monomer concentrations. It was found that α is not a monotonic function of . As is increased, α first decreases up to about and remains constant in a narrow range of , but then it increases continuously. The -dependence of α is due to the variation of the network chain length N depending on the gel preparation concentration. In the range of below 0.1, N follows the scaling relationship , while at higher concentrations, N varies only slightly with . The increase of α with N obeys the relation , as predicted by the Flory-Rehner theory.     

Synthesis and application of novel ionic phosphine ligands with a cobaltocenium backbone

Six novel ionic phosphine ligands with a cobaltocenium backbone, 1,1′-bis(dicyclohexylphosphino) cobaltocenium hexafluorophosphate () (1a), 1,1′-bis(di-iso-propylphosphino) cobaltocenium hexafluorophosphate () (2a), 1,1′-bis(di-tert-butylphosphino) cobaltocenium hexafluorophosphate () (3a), and the monophosphine ligand (Cc⁺ = cobaltocenium; R = Cy, 1b; R = i-Pr, 2b; R = t-Bu, 3b) were synthesized and characterized by elemental analysis, spectroscopy, and X-ray diffraction techniques. These ligands are air-stable and useful for Suzuki coupling reactions in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (), enabling high catalytic activity.