Sensitized photo-oxidation of methylcyclohexane as a thin film on seawater by irradiation with natural sunlight

Methylcyclohexane dissolved in and forming a thin film on purified seawater with traces of anthraquinone added as triplet sensitizer was exposed to natural sunlight in a quartz flask. The water was circulated through a glass cartridge filled with Amberlite XAD-2 for the concentration of reaction products which were identified by GC/MS after elution and silica gel chromatography. They included isomeric methylcyclohexanols as the principal components, primary hydroperoxides, a tentatively identified secondary peroxide, methylcyclohexanones, and acyclic ketones. Mass spectra and mechanisms are discussed as well as possible biological consequences of the formation of these compounds.     

C(methyl)–H ⋅ ⋅ ⋅ π(aryl) Interaction Stabilizing Molecular Conformation. X-Ray Crystal Structure of an Inclusion Compound of a Nonprotic Host with Nitromethane Guest

In the cocrystal formation of a nonprotic polar (host) molecule (1) with nitromethane (guest) several weak, but directional, intermolecular interactions have vital importance. The endo conformation of the (N)-xylene group of the polycyclic succinimide-based host 1 is stabilized by a C_methyl $---$ H ??? π interaction [C ??? π /H ??? π distances are 3.554(7)/2.57 Å, the C $---$ H ??? π angle is 159^○], and the crystal packing is governed by dipole–dipole type interhost (C $ =$ )O ??? C( $ =$ O) connection [C ??? O $ =$ 3.000(5) Å and <C $ =$ O ??? C $ =$ 159.8(3)^○] in conjunction with possible C $---$ H ??? O interactions [with C ??? O distances ranging between 3.20 and 3.50 Å] involving the polar groups of both host and guest. Crystal data: 1 ??? nitromethane (1:1), C₂₆H₂₁O₂ N ? CH₃NO₂, M _w = 440.50, P2 ₁/n, a = 14.143(1), b = 7.973(1), c = 20.291(2) Å, β = 95.183(9)^○, Z = 4, D _c = 1.2840(2) g cm^?3, R = 0.055 for 1709 reflections.     

Photoelectron spectroscopy of fullerene dianions C76(2-), C78(2-), and C84(2-)

We report laser photoelectron spectra of the doubly negatively charged fullerenes C(76) (2-), C(78) (2-), and C(84) (2-) at 2.33, 3.49, and 4.66 eV photon energy. From these spectra, second electron affinities and vertical detachment energies, as well as estimates for the repulsive Coulomb barriers are obtained. These results are discussed in the context of electrostatic models. They reveal that fullerenes are similar to conducting spheres, with electronic properties scaling with their size. The experimental spectra are compared with the accessible excited states of the respective singly charged product ions calculated in the framework of time dependent density functional theory.     

Resonant two photon ionization of phenanthrene via its transientS 2 state

We report the vibrationally resolved photoelectron spectrum of phenanthrene obtained by two photon ionization via theS ₂ electronic state. The experiments were performed with picosecond laser pulses with a bandwidth sufficiently large to span a significant fraction of the intermediate resonance state. Therefore the photoelectron spectrum is dominated by signal corresponding to the unrelaxed intermediate resonance, in spite of this state's 420 fs lifetime.     

Fluorescent and electroactive cyclic assemblies from perylene tetracarboxylic acid bisimide ligands and metal phosphane triflates

Tetraaryloxy-substituted perylene tetracarboxylic acid bisimides with one or two 4-pyridyl receptor substituents at the imide functionality were synthesized and employed in transition metal directed self-assembly with Pd(II) and Pt(II) phosphane triflates. Upon mixing of the components, quantitative formation of functional molecular square-type complexes containing four dye molecules and model complexes of a 2:1 (perylene bisimide ligand:transition metal ion) stoichiometry was observed. The isolated metallosupramolecular squares were characterized by 1H and 31P [1H] NMR spectroscopy as well as conventional electrospray ionization (ESI) and ESI-FTICR mass spectrometry, which gave evidence for the structure and the high stability of these giant cyclic dye assemblies (molecular weight (3a) 8172, Pt-Pt corner diagonal ca. 3.4 nm). Studies of the optical absorption and fluorescence properties and the electrochemistry and spectroelectrochemistry of both the perylene bisimide ligands and the perylene bisimide metal complexes show that Pt(II) coordination does not interfere with the optical and electrochemical properties of the perylene bisimide ligands; this gives squares with high fluorescence quantum yields (phiF (3a)=0.88) and three fully reversible redox couples. The latter could be unambiguously related to quantitative formation of perylene bisimide radical cations (E1/2 = +0.93 V vs. Fc/Fc+), radical anions (E1/2= - 1.01 V vs. Fc/Fc+), and dianions (E1/2 = -1.14 V vs. Fc/Fc+); these redox reactions change the charge state of the cyclic assembly from +12 to zero. In contrast, Pd(II) coordination influenced the electrochemical properties of the assembly because of an irreversible palladium reduction at E1/2= -1.15 V versus Fc/Fc+. Finally, dynamic ligand exchange processes between different metallosupramolecular assemblies were investigated by multinuclear NMR and electrospray mass spectrometry. These studies confirmed the reversible nature of the pyridine-Pt(II)/Pd(II) coordination process.     

Atomic and molecular fluorescence with long radiative decay times from laser excited Na2

Na₂ is excited (B¹Π_u←X¹Σ _g ⁺ ) in the presence of noble gases (20–700 Torr). The Na₂ fluorescence decay shows two lifetimes: a short component which corresponds to the well known lifetime of Na₂ in the B¹Π_u state [1], and a long component with a lifetime of about 0,1 μs which depends strongly on the noble gas density [2]. The same long lived radiative decay is also seen via the Na resonance fluorescence Na(3²S)←Na(3²P).     

Kinetics of Desolvation of Related Organic Inclusion Compounds

Abstract

This study dealt mainly with the structure-reactivity relationship of selected organic inclusion compounds. The crystal structures of the inclusion compounds of three related hosts, 2,2′–bis(2,7–di-tert-butyl-9–hydroxy-9–fluorenyl)biphenyl, 2,2′–bis (2,7–dichloro-9–hydroxy-9–fluoienyl)biphenyl and 2, 2′–bis(2,7-dibromo-9–hydroxy-9–fluorenyl)biphenyl with 1,4–dioxane (Compound 1), 1,3–dioxane (Compound 2) and 1,3–dioxolane (Compound 3) respectively were elucidated, using single crystal X-ray crystallography. It was found that the guests were either located in channels or constricted channels (cavities), formed by the host framework. The kinetics of desolvation of these compounds were studied and their activation energies were compared.     

The mesomorphic behaviour of cyanopropylalkyldimethylammonium bromides

Abstract

A homologous series of N-cyanopropyl-N-alkyl-N,N-dimethylammonium bromides was synthesized and characterized. Its thermotropic liquid crystalline behaviour was studied by differential scanning calorimetry, polarizing optical microscopy, dilatometry, and X-ray diffraction. A smectic A mesophase was thus identified. The smectic layers were found to be formed of two ionic planes alternately separated by sub-layers of disordered alkyl chains and cyanopropyl groups. The smectic structure was compared with that of the crystal at room temperature and also that of the smectic T structure of the N,N-dialkyl-N,N-dimethylammonium bromides already described in the literature.