Structure‐Dependent Photoinduced Electron Transfer in Fullerodendrimers with Light‐Harvesting Oligophenylenevinylene Terminals

Oligophenylenevinylene (OPV)‐terminated phenylenevinylene dendrons G1 – G4 with one, two, four, and eight “side‐arms”, respectively, were prepared and attached to C₆₀ by a 1,3‐dipolar cycloaddition of azomethine ylides generated in situ from dendritic aldehydes and N‐methylglycine. The relative electronic absorption of the OPV moiety increases progressively along the fullerodendrimer family C₆₀G1 – C₆₀G4 , reaching a 99:1 ratio for C₆₀G4 (antenna effect). UV/Vis and near‐IR luminescence and transient absorption spectroscopy was used to elucidate photoinduced energy and electron transfer in C₆₀G1 – C₆₀G4 as a function of OPV moiety size and solvent polarity (toluene, dichloromethane, benzonitrile), taking into account the fact that the free‐energy change for electron transfer is the same along the series owing to the invariability of the donor–acceptor couple. Regardless of solvent, all the fullerodendrimers exhibit ultrafast OPV→C₆₀ singlet energy transfer. In CH₂Cl₂, the OPV→C₆₀ electron transfer from the lowest fullerene singlet level (¹C₆₀*) is slightly exergonic (ΔG_CS≈0.07 eV), but is observed, to an increasing extent, only in the largest systems C₆₀G2 – C₆₀G4 with lower activation barriers for electron transfer. This effect has been related to a decrease of the reorganization energy upon enlargement of the molecular architecture. Structural factors are also at the origin of an unprecedented OPV→C₆₀ electron transfer observed for C₆₀G3 and C₆₀G4 in apolar toluene, whereas in benzonitrile, electron transfer occurs in all cases. Monitoring of the lowest fullerene triplet state by sensitized singlet oxygen luminescence and transient absorption spectroscopy shows that this level is populated through intersystem crossing and is not involved in photoinduced electron transfer.     

Two-particle friction in a mesoscopic solvent

The effects of hydrodynamic interactions on the friction tensors for two particles in solution are studied. The particles have linear dimensions on nanometer scales and are either simple spherical particles interacting with the solvent through repulsive Lennard-Jones forces or are composite cluster particles whose atomic components interact with the solvent through repulsive Lennard-Jones forces. The solvent dynamics is modeled at a mesoscopic level through multiparticle collisions that conserve mass, momentum, and energy. The dependence of the two-particle relative friction tensors on the interparticle separation indicates the importance of hydrodynamic interactions for these nanoparticles.     

An efficient closed-shell singles and doubles coupled-cluster method

A reformulated set of equations for the closed-shell singles and doubles coupled-cluster (CCSD) method is presented. A computational cost of n_v⁴n₀²+7n_v³n₀³+1n_v²n₀⁴ for the n⁶ steps is obtained, where n_v is the number of virtual molecular orbitals included in the CCSD procedure, n₀ is the number of doubly occupied molecular orbitals and n=n₀+n_v. Test calculations for the cis and trans isomers of FNNF and planar and pyramidal CH₃⁻ are presented. Equilibrium structures determined with large Gaussian basis sets at the second-order Møller-Plesset (MP2) perturbation level of theory are reported and used for the other electron correlation methods. With the largest one-particle basis set (144 contracted Gaussian functions), the equilibrium geometries of cis- and trans-FNNF agree with experiment. Based on analyses of planar and pyramidal CH₃⁻ wavefunctions and the calculated inversion barrier, it is suggested that the molecular anion may not exist in a planar configuration but that autodetachment of an electron occurs before the transition state is reached. Comparisons of our new CCSD procedure demonstrate that coupled-cluster methods are not significantly more expensive than similar electron correlation techniques.     

A zwitterion of 1,5‐bis­(2‐hydroxy­benzamido)‐3‐aza­pentane: a two‐dimensional hydrogen‐bonding network involving dimers

The title compound, 2‐{N‐[2‐(2‐hydroxy­benzamido)ethyl­ammonio­ethyl]amino­carbon­yl}phenolate, C₁₈H₂₁N₃O₄, crystallizes in a zwitterionic form as a result of inter­molecular proton transfer and possesses a negatively charged phenolate group and a protonated amino group. The 2‐hydroxy­benzamide and 2‐(amino­carbonyl)­phenolate moieties attached to the two ends of the C—C—N—C—C backbone adopt a cis conformation in relation to this backbone. All N‐ and O‐bound H atoms are involved in hydrogen‐bond formation; the zwitterions are first linked into head‐to‐tail dimers, which are further organized into a two‐dimensional network parallel to the crystallographic bc plane.     

Temperature and Oxygen Partial Pressure Dependences of the Surface Tension of Liquid Sn–Ag and Sn–Cu Lead-free Solder Alloys

Temperature dependence of the surface tension of liquid Sn–Ag and Sn–Cu base lead-free solder alloys and oxygen partial pressure dependence of liquid Sn–Ag alloy were evaluated using the experimental data obtained, respectively, by the constrained drop method and the sessile drop method in the previous studies [1, 2]. The temperature dependences of the surface tension have maximum positive values when the mol fraction of Ag and Cu is about 0.7, while those for pure liquid Sn, Ag, and Cu have negative values. The calculated values based on Butler’s equations were found to be in reasonable agreement with those of the experimental data. The oxygen partial pressure dependences of the surface tension of liquid Sn–Ag alloys at 1253 K have a minimum value when the mol fraction of Ag is about 0.9 and the oxygen partial pressure is less than about 10⁻¹³ atm. From this, it is considered that the oxygen adsorption increased by adding Ag to Sn when the mol fraction of Ag is less than 0.9.     

Charged particle evaporation from compound nuclei formed by bombardment of58Ni with 70 MeV16O ions II

The experimental data have been compared with the result of extensive compound nucleus calculations based on the statistical theory. The shapes and the absolute cross sections for the high energy parts of the proton- and -spectra are reproduced with a level density parametera 0·11 A MeV^–1 and a moment of inertiaJ1·3J _rig. The same parameters fairly well reproduce the angular distributions corresponding to the high energy parts of the spectra whereas deviations between theory and experiment are observed for the lower energies where particles emitted by higher order processes contribute. The observed total cross section for emission of an -particle is 500 mb or 1·7 times calculated value. For protons the corresponding numbers are 2313 mb and 3·0. The increase in cross section is ascribed to the process in which several particles are evaporated. Various methods are discussed for determination of the average orbital angular momentum of the emitted particle or the average spin of the daughter nucleus.On leave fromFaculty of Matematics and Physics, Charles University, Prague, Czechoslovakia.     

Comparison of Si-O-C interfacial bonding of alcohols and aldehydes on Si(111) formed from dilute solution with ultraviolet irradiation

Aliphatic alcohols and aldehydes were reacted with the Si(111)-H surface to form Si-O-C interfacial bonds from dilute solution by using ultraviolet light. The resulting monolayers were characterized by using transmission infrared spectroscopy, spectroscopic ellipsometry, and contact angle measurements. The effect of different solvents on monolayer quality is presented. The best monolayers were formed from CH(2)Cl(2). The optimized monolayers were thoroughly characterized to determine the film structure and monolayer stability. The UV-promoted, alcohol-functionalized, and aldehyde-functionalized monolayers are of comparable quality to those previously prepared by other means. Although both molecules are tethered through a Si-O-C bond, the film reactivity is distinctly different with the aldehyde films being more chemically resistant. The differences in chemical reactivity, vibrational spectra, hydrophobicity, and ellipsometric thickness between the alcohol and aldehyde monolayers are attributed to a difference in molecular coverage and monolayer formation.     

Synthesis of 2‐Dihydrooxadiazolinyl Chromones

Reactions of the substituted 2‐formyl chromones with aroylhydrazines gave corresponding 2‐(aroylhydrazonomethylidyne) chromones. Then 2‐(3′‐acetyl‐5′‐aryl‐2′,3′‐dihydro‐1′,3′,4′‐oxadiazol‐2′‐yl) chromones were prepared by these 2‐(aroylhydrazonomethylidyne) chromones under refluxing with Ac₂O. All target compounds were characterized through elemental analysis and IR, ¹H NMR, MS.     

Mössbauer Studies on Spin State of the Thermal Decomposition of Substituted Tris (2-Pyridylimine) Iron (II) Thiocyanate

The spin states of iron (II) in FeL₂(NCS)₂ produced from the thermal decomposition of FeL₈(NCS)₂ (L=2-py-CR₁=NR₂, R₁ or R₂=H, Me(CH₃), Ph) under nitrogen atmosphere are investigated by means of Mössbauer spectroscopy and magnetic measurements. It was found that the spin states of iron (II) in substitutited bis (2-pyridylimine) iron (II) thiocyanate are included: intermediate-spin (³T₁, S=1), mixed-spin of ⁵T₂(S=2)+³T₁ and spin incomplete transition of ⁵T₂?³T₁.