Synthesis and 1H, 19F NMR spectroscopic characterization of (pentafluorophenyl)3-n (pyrazol-1-yl-tetrafluorophenyl)n=1,2 porphyrins

Three new porphyrins bearing in the meso positions 4-(pyrazol-1-yl)-2,3,5,6-tetrafluorophenyl substituents have been prepared and characterized by nmr spectroscopy.     

Gelfand numbers of operators with values in a Hilbert space

In the paper we prove two inequalities involving Gelfand numbers of operators with values in a Hilbert space. The first inequality is a Rademacher version of the main result in [Pa-To-1] which relates the Gelfand numbers of an operator from a Banach spaceX intol ₂ ⁿ with a certain Rademacher average for the dual operator. The second inequality states that the Gelfand numbers of an operatoru froml ₁ ^N into a Hilbert space satisfy the inequality

Strong, low-energy two-photon absorption in extended amine-terminated cyano-substituted phenylenevinylene oligomers

Three quadrupolar oligophenylenevinylenes with five rings in the conjugated backbone, terminal donor groups, and various acceptors and/or donors along the backbone were synthesized and their two-photon spectroscopic properties investigated. These chromophores exhibit large two-photon absorption cross sections over a wide wavelength range and two distinct peaks, the strongest of which (deltamax > 3600 GM) is observed at 960-970 nm, a wavelength close to twice the value of the linear absorption maximum (2lambda(1)max). The findings on these chromophores are compared with those for analogous molecules with shorter conjugation length, for which the main two-photon band is at significantly shorter wavelength than 2lambda(1)max.     

Reactions de photoaddition de benzo[b]selenophenes avec l'acetylene dicarboxylate de methyle et avec le dichloro-1,2 ethylene

Photoirradiated in presence of acetophenone, benzo[b]selenophene and its 3-methyl derivative add to dimethyl acetylenedicarboxylate. In each ease, the primary reaction product is unstable and has not been isolated. Photoexeited in its triplet state (the energy of which is in the neighbourhood of 69 $\text{kcal}\text{mole}$) benzo[b]selenophene and its 2- and 3-methyl, 2,3 dimethyl, 3 acetoxy and 2-methyl-3-acetoxy derivatives add to 1,2 dichloroethylene leading to cyclobutanes. Neither cyclo-addition occurs in absence of photosensitiser. Single-crystal X-ray analysis gave the structures of the two adducts of 3-acetoxybenzo[b]selenophene with trans-1,2-dichloroethylene. In both compounds the chlorine atoms are trans.     

A straightforward preparation of amino–polystyrene resin from Merrifield resin

Azidomethyl–polystyrene, obtained by nucleophilic substitution of chloromethyl–polystyrene, undergoes a Schmidt rearrangement when treated with trifluoromethanesulfonic acid, affording amino–polystyrene. To assess its loading and reactivity the resin is used as a support for the preparation of triazene-linked amine.     

FLUORESCENCE AND PHOTOCHEMISTRY OF OLIGOCYTIDYLIC AND POLYCYTIDYLIC ACIDS IN AQUEOUS SOLUTION

Abstract —In addition to the monomer-like fluorescence, a long-wavelength emission (Λ^max_em= 410 nm) has been detected in the dinucleoside 5'-5' pyrophosphate (CppC) at room temperature. This emission looks very similar to that previously reported for the acidic forms of Poly C (Poly C. Poly C⁺ and Poly I. Poly C. Poly C⁺). Only the monomer-like emission (Λ^max_em= 330 nm) can be detected in neutral Poly C, acidic CppC, and the neutral or protonated forms of the dinucleoside phosphate CpC.A correlation between the room temperature fluorescence of oligo and polycytidylic acids and their photochemical behaviour is found. Irradiation of all the polymeric samples at both neutral and acid pH results in the formation of minor photoproducts. They have been characterized by their absorbance (in the range 300–400 nm) and their fluorescence spectra. The same product is obtained in all cases where the monomer-like fluorescence only is detected. Distinct products are formed in neutral CppC and in the acidic Poly C forms.
The results are discussed with respect to the conformation of the oligo and polycytidylic acids and possible relationships between the 410–420 nm emission and adduct formation. An excimer is proposed as a common, intermediate excited state in both radiative deactivation and adduct formation in neutral CppC and the acidic Poly C forms.     

Unprecedented, fully recyclable, solid-supported reagent for the kinetic resolution of racemic amines through enantioselective N-acetylation

The high-yielding synthesis and application of the first polymer supported reagent for the kinetic resolution (KR) of amines through enantioselective acetylation is described; this new supported chiral reagent allows the KR of primary amines with excellent selectivities at room temperature; moreover, this supported approach is highly efficient as the Merrifield-supported chiral scaffold can be quantitatively recovered and recycled.     

Solvation of uranyl(II), europium(III) and europium(II) cations in "basic" room-temperature ionic liquids: a theoretical study

We report a molecular dynamics study of the solvation of UO2(2+), Eu3+ and Eu2+ ions in two "basic" (Lewis acidity) room-temperature ionic liquids (IL) composed of the 1-ethyl-3-methylimidazolium cation (EMI+) and a mixture of AlCl4- and Cl- anions, in which the Cl-/AlCl4- ratio is about 1 and 3, respectively. The study reveals the importance of the [UO2Cl4]2- species, which spontaneously form during most simulations, and that the first solvation shell of europium is filled with Cl- and AlCl4- ions embedded in a cationic EMI+ shell. The stability of the [UO2Cl4]2- and [Eu(III)Cl6]3- complexes is supported by quantum mechanical calculations, according to which the uranyl and europium cations intrinsically prefer Cl- to the AlCl4- ion. In the gas phase, however, [Eu(III)Cl6]3- and [Eu(II)Cl6]4- complexes are predicted to be metastable and to lose two to three Cl- ions. This contrasts with the results of simulations of complexes in ILs, in which the "solvation" of the europium complexes increases with the number of coordinated chlorides, leading to an equilibrium between different chloro species. The behavior of the hydrated [Eu(OH2)8]3+ complex is considered in the basic liquids; the complex exchanges H2O molecules with Cl- ions to form mixed [EuCl3(OH2)4] and [EuCl4(OH2)3]- complexes. The results of the simulations allow us to better understand the microscopic nature and solvation of lanthanide and actinide complexes in "basic" ionic liquids.