Carbon–Phosphorus Coupling from C^N Cyclometalated AuIII Complexes

With the aim of exploiting new organometallic species for cross-coupling reactions, we report here on the Au^III-mediated C_aryl−P bond formation occurring upon reaction of C^N cyclometalated Au^III complexes with phosphines. The [Au(C^N)Cl₂] complex 1 featuring the bidentate 2-benzoylpyridine (C^CON) scaffold was found to react with PTA (1,3,5-triaza-7-phosphaadamantane) under mild conditions, including in water, to afford the corresponding phosphonium 5 through C−P reductive elimination. A mechanism is proposed for the title reaction based on in situ ³¹P{¹H} NMR and HR-ESI-MS analyses combined with DFT calculations. The C−P coupling has been generalized to other C^N cyclometalated Au^III complexes and other tertiary phosphines. Overall, this work provides new insights into the reactivity of cyclometalated Au^III compounds and establishes initial structure–activity relationships to develop Au^III-mediated C−P cross-coupling reactions.     

Photorefractive control of surface plasmon polaritons in a hybrid liquid crystal cell

We present a photorefractive hybrid liquid crystal system that allows strong photorefractive effects on surface plasmon polaritons. We demonstrate its capability to couple energy between two 1.03 eV surface plasmon polariton modes with an efficiency of 25.3±2.3%. We present the energy and grating pitch dependence of the diffraction and a model that can qualitatively explain them.     

Computational study of the interaction of proflavine with d(ATATATATAT)2 and d(GCGCGCGCGC)2

The interaction of proflavine (PR) with two B-DNA decamers of alternating AT and GC sequence, called [deca(dG-dC)]₂ and [deca(dA-dT)]₂, respectively, was computationally investigated by the ONIOM method, exploiting a three-layer QM/QM/MM hybrid approach. The highest level QM method was applied to the model system, which comprises the intercalation site (5th and 6th base pairs) and the inserted PR molecule. The connecting sugar phosphate backbone was added in the medium layer region. Both higher and medium level layers, differing in the size of the basis set used, were treated by the DFT MPWB1K functional. The full system in the lower layer was described by the empirical AMBER force field. The calculated values of the interaction energy of PR with [deca(dG-dC)]₂ and [deca(dA-dT)]₂, as well as with the dinucleotides d(GpC)₂, and d(ApT)₂, the latter considered either in vacuo and in the mimicked water solvent, support for a static higher affinity toward G-C compared to the A-T DNA base sequences, in agreement with structural results from crystallographic studies. Furthermore, the different structural characteristics of the [deca(dG-dC)]₂/PR complex compared to those of the [deca(dA-dT)]₂/PR, furnish a possible interpretation of apparently controversial experimental thermodynamic data, explained in terms of two possible modes of non-covalent binding of ligands with DNA, namely intercalation and external binding, respectively.     

Mixtures of strongly interacting bosons in optical lattices

We investigate the properties of strongly interacting heteronuclear boson-boson mixtures loaded in realistic optical lattices, with particular emphasis on the physics of interfaces. In particular, we numerically reproduce the recent experimental observation that the addition of a small fraction of 41K induces a significant loss of coherence in 87Rb, providing a simple explanation. We then investigate the robustness against the inhomogeneity typical of realistic experimental realizations of the glassy quantum emulsions recently predicted to occur in strongly interacting boson-boson mixtures on ideal homogeneous lattices.     

Release time calculations for the SPES direct UCx target

A Direct Target for a mid-term RIB ISOL-type facility is being developed at LNL, in the framework of the R&D for the SPES project [1]. Using a 40 MeV proton beam impinging on a UCx thick target of 2.5 g/cm³ density, a production rate of 10¹³ in target fissions per second is expected [2]. The crucial point, when short-lived isotopes are produced in the target, is to build systems (target + ion source) with good release properties and high efficiency. Monte Carlo simulations were performed using the GEANT4 toolkit [3] and the RIBO code [4] in order to optimize our target geometry and to estimate the average release time.     

On a generalization of Kantor's likeable planes

Generalizing an idea of Kantor [7], Johnson and Wilke [5] introduced elusive sets of functions over GF(q) to represent translation planes of order q ² that admit a collineation group of order q ² in the linear translation complement and whose kern contains GF(q). In this paper we determine explicitly all elusive sets for q even. We obtain another translation plane of order 8².Deicated to Professors Adriano Barlotti and Luigi Antonio Rosati on the occasion of their 60th birthdayThis research was supported in part by a grant from the M.P.I. (40% funds).     

On the reactivity of organometallic compounds towards functional substrates : IV. The reaction of aliphatic 1-alkynes with triisobutyl-aluminum: Dependence on the structure of the acetylenic substrate

The reaction between triisobutylaluminum and aliphatic 1-alkynes having alkyl groups of different structure on the 3-carbon atom has been investigated. At room temperature and in the absence of solvents, products which correspond to metallation, reduction and carbalumination processes, are isolated after hydrolysis. The extent of such reactions, and in particular the regiospecificity of the carbalumination is dependent on the experimental conditions adopted and on steric factors associated with the structure of the 1-alkyne used. On the basis of these results and the complete stereospecificity of the reaction when (+)(S-3,4-dimethyl-1-pentyne is used, possible mechanisms are discussed.     

Photophysics of octabutoxy phthalocyaninato-Ni(II) in toluene: ultrafast experiments and DFT/TDDFT studies

Reported herein is a combination of experimental and DFT/TDDFT theoretical investigations of the ground and excited states of 1,4,8,11,15,18,22,25-Octabutoxyphthalocyaninato-nickel(II), NiPc(BuO)(8), and the dynamics of its deactivation after excitation into the S(1)(pi,pi) state in toluene solution. According to X-ray crystallographic analysis NiPc(BuO)(8) has a highly saddled structure in the solid state. However, DFT studies suggest that in solution the complex is likely to flap from one D(2)(d)-saddled conformation to the opposite one through a D(4)(h)-planar structure. The spectral and kinetic changes for the complex in toluene are understood in terms of the 730 nm excitation light generating a primarily excited S(1) (pi,pi) state that transforms initially into a vibrationally hot (3)(d(z)2,d(x)2(-)(y)2) state. Cooling to the zeroth state is complete after ca. 8 ps. The cold (d,d) state converted to its daughter state, the (3)LMCT (pi,d(x)2(-)(y)2), which itself decays to the ground state with a lifetime of 640 ps. The proposed deactivation mechanism applies to the D(2)(d)-saddled and the D(4)(h)-planar structure as well. The results presented here for NiPc(BuO)(8) suggest that in nickel phthalocyanines the (1,3)LMCT (pi,d(x)2(-)(y)2) states may provide effective routes for radiationless deactivation of the (1,3)(pi,pi) states.     

A "catch and release" strategy for the parallel synthesis of 2,4,5-trisubstituted pyrimidines

A resin capture and release strategy for making a combinatorial array of 2,4,5-trisubstituted pyrimidines is demonstrated by capturing beta-ketoesters and beta-ketoamides on a solid-supported piperazine. Through a cyclocondensation reaction, the solid-supported enaminone is reacted with several guanidines under heating or microwave irradiation affording the corresponding pyrimidines in good yield and chemical purity directly on solution. After this final step, the support can be effectively recycled.