Thermally Induced Synthesis of Anthracene-, Pyrene- and Naphthalene-Fused Porphyrins

The synthesis of π-extended porphyrins containing anthracenyl moieties still represents an important challenge. Here, we report on the synthesis of a series of unsubstituted naphthyl-, pyrenyl- and anthracenyl-fused zinc porphyrin derivatives. To this aim, meso-substitued porphyrins are synthesized and the fusion of the PAHs (Polycyclic Aromatic Hydrocarbon) on the β-positions are performed through thermally induced dehydro-aromatization. The fused zinc-porphyrin derivatives are fully characterized and their optical absorption and photoluminescence properties are reported. We also demonstrate that zinc can be removed from the porphyrin core, giving rise to pure C, H, N materials. This work constitutes the first step towards the synthesis of the fully-fused tetra-anthracenylporphyrin.     

Monitoring of the Pre-Equilibrium Step in the Alkyne Hydration Reaction Catalyzed by Au(III) Complexes: A Computational Study Based on Experimental Evidences

The coordination ability of the [(ppy)Au(IPr)]²⁺ fragment [ppy = 2-phenylpyridine, IPr = 1,3-bis(2,6-di-isopropylphenyl)-imidazol-2-ylidene] towards different anionic and neutral X ligands (X = Cl⁻, BF₄⁻, OTf⁻, H₂O, 2-butyne, 3-hexyne) commonly involved in the crucial pre-equilibrium step of the alkyne hydration reaction is computationally investigated to shed light on unexpected experimental observations on its catalytic activity. Experiment reveals that BF₄⁻ and OTf⁻ have very similar coordination ability towards [(ppy)Au(IPr)]²⁺ and slightly less than water, whereas the alkyne complex could not be observed in solution at least at the NMR sensitivity. Due to the steric hindrance/dispersion interaction balance between X and IPr, the [(ppy)Au(IPr)]²⁺ fragment is computationally found to be much less selective than a model [(ppy)Au(NHC)]²⁺ (NHC = 1,3-dimethylimidazol-2-ylidene) fragment towards the different ligands, in particular OTf⁻ and BF₄⁻, in agreement with experiment. Effect of the ancillary ligand substitution demonstrates that the coordination ability of Au(III) is quantitatively strongly affected by the nature of the ligands (even more than the net charge of the complex) and that all the investigated gold fragments coordinate to alkynes more strongly than H₂O. Remarkably, a stabilization of the water-coordinating species with respect to the alkyne-coordinating one can only be achieved within a microsolvation model, which reconciles theory with experiment. All the results reported here suggest that both the Au(III) fragment coordination ability and its proper computational modelling in the experimental conditions are fundamental issues for the design of efficient catalysts.     

Atomic orbitals with angularly dependent Z eff to be used in molecular orbitals calculations

A new type of atomic orbital is proposed for use in molecular problems of quantum mechanics. This orbital is formally similar to Slater's orbitals but is characterized by an effective nuclear charge Z _eff which is an explicit function of the angles ? and φ. The fundamental state of the molecule H₂ ⁺ is studied using such an orbital.     

Mean-field versus microconvection effects in nanofluid thermal conduction

Transient hot-wire data on thermal conductivity of suspensions of silica and perfluorinated particles show agreement with the mean-field theory of Maxwell but not with the recently postulated microconvection mechanism. The influence of interfacial thermal resistance, convective effects at microscales, and the possibility of thermal conductivity enhancements beyond the Maxwell limit are discussed.     

Base‐dependent selectivity of an SNAr reaction

A detailed kinetic analysis and computational study of an S_NAr reaction between 2,5,6‐trifluoronicotinonitrile, 2 , and the ambident 3‐isopropoxy‐1H‐pyrazol‐5‐amine, 3 , is presented. The selectivity with respect to the reaction at the primary amino group of 2 , to give the desired product, 2,5‐difluoro‐6‐[(3‐isopropoxy‐1H‐pyrazol‐5‐yl)amino]nicotinonitrile, 1 , is strongly dependent upon reaction conditions. Reaction is found to proceed via both uncatalysed and base catalysed routes, and selectivity towards 1 is strongly enhanced in the presence of the base diazabicyclo[2,2,2]octane (DABCO). Computational studies in tetrahydrofuran solution at the B3LYP/6‐31G* level of theory have provided valuable insight into alternative kinetically indistinguishable reaction pathways. The results suggest that for reaction at the primary amino group, proton removal by DABCO accompanying amine addition allows avoidance of a high‐energy, zwitterionic Meisenheimer intermediate. Reactions at the alternative pyrazole nitrogen atoms are less sensitive to the presence of base because of stabilisation of the Meisenheimer zwitterions by intramolecular hydrogen bonding. Copyright © 2010 John Wiley & Sons, Ltd.     

Phase separation and pattern formation in a binary Bose-Einstein condensate

The miscibility-immiscibility phase transition in binary Bose-Einstein condensates (BECs) can be controlled by a coupling between the two components. Here we propose a new scheme that uses coupling-induced pattern formation to test the Kibble-Zurek mechanism (KZM) of topological-defect formation in a quantum phase transition. For a binary BEC in a ring trap we find that the number of domains forming the pattern scales as a function of the coupling quench rate with an exponent as predicted by the KZM. For a binary BEC in an elongated harmonic trap we find a different scaling law due to the transition being spatially inhomogeneous. We perform a "quantum simulation" of the harmonically trapped system in a ring trap to verify the scaling exponent.     

Investigation of the 40Ar + 197Au, 238U systems at 44 MeV/u

We have measured the angular correlation between two fragments emitted in the reactions Ar + Au and Ar + U at 44 MeV/u at GANIL. The aim was to investigate the amount of initial linear momentum transferred from the projectile to a fissioning nucleus. It turned out that this amount is much smaller than can be extrapolated from previous experiments. Furthermore, the probability of forming a fissioning nucleus is very small.     

Model for the evolution of hot and compressed spherical nuclei

A hydrodynamical approach and the Thomas Fermi approximation have been used to study the evolution of hot and compressed nuclei. Spherical symmetry was assumed in the calculation. The dynamical equations have been transformed into “Schrödinger like” equations (using the Madelung transformation) and were solved numerically. Dissipation was simulated in the same way as in the Navier-Stokes equation by introducing shear and bulk viscosities. Global as well as local thermal equilibrium have been studied. The model has been applied to small amplitude oscillations (the breathing mode) and to the stability of hot and compressed nuclei. It was found that compression is more efficient to break nuclei than thermal excitation. The relaxation time for global equilibrium was estimated to be of the order of 10^?22 s. It was found that the results obtained in the case of global and local thermal equilibrium are very similar.     

K-stability of constant scalar curvature Kähler manifolds

We show that a polarised manifold with a constant scalar curvature Kähler metric and discrete automorphisms is K-stable. This refines the K-semistability proved by S.K. Donaldson.     

A simple leading particle explanation for linear momentum transfer systematics

A simple formula based on leading particle models of nucleon-nucleon collisions is used to evaluate the average momentum transfer in central heavy ion collisions at energies from 20 to 150 MeV/u. This formula, which reproduces a number of the features of the observed systematics, offers a straightforward explanation for the approximate universality of fractional linear momentum transfer as a function of velocity, the dependence of fractional momentum transfer on target mass and the greater fractional momentum transfer of the proton as compared to heavy ion projectiles.