Tetrakis(2-hydroxyphenyl)ethene and derivatives. A structurally preorganized tetradentate ligand system for polymetallic coordination chemistry and catalysis

A topologically unique, conformationally constrained tetradentate ligand system for polymetallic coordination chemistry has been developed: tetrakis(2-hydroxyphenyl)ethene (1a) and substituted derivatives. The design exploits the planarity of the tetraphenylethylene core to impart rigidity to the roughly square oxygen binding array, while maintaining a degree of conformational mobility associated with rotation about the aryl-ethylene carbon-carbon bonds. Tetrakis(2-hydroxyphenyl)ethene derivatives are designed to promote multiple metal bridging over chelating coordination modes. The ligand is synthesized from anisole or 4-tert-butylanisole in four steps via the 2,2'-dimethoxybenzophenone hydrazones 4a,b. The sterically hindered ortho-substituted tetraphenylethylene core is produced in high yield by acid-catalyzed decomposition of the corresponding diaryl diazomethane prepared in situ by oxidation of the hydrazone using nickel peroxide. Deprotection of the methyl ethers using boron tribromide gives tetrakis(2-hydroxyphenyl)ethene (1a), characterized by X-ray crystallography, and tetrakis(5-tert-butyl-2-hydroxyphenyl)ethene (1b). Sterically isolating substituents in the 3-position can be installed via Claisen rearrangement/hydrogenation, providing tetrakis(3-n-propyl-2-hydroxyphenyl)ethene (6) efficiently. To illustrate potential applications of this unprecedented ligand class, two coordination complexes are reported, including tetrakis(2-diethylaluminoxyphenyl)ethene (8), a structurally robust eight-membered-ring aluminum/oxygen crown complex characterized both in solution and in the solid state.     

Saturation in degenerate four wave mixing: The dressed-atom approach

A dressed atom approach of saturation in degenerate four-wave mixing is presented. Because of the Doppler-shift of the pump and probes waves frequencies, a resonance between levels of the dressed atom occurs for two velocity groups. When the Rabi frequency Ω₁ is smaller than the Doppler width ku, these resonant terms give the essential contribution to the signal which is analytically calculated. When Ω₁ å ku, the signal is expected to be much smaller.     

Bright optical lattices in a longitudinal magnetic field. Experimental study of the oscillating and jumping regimes

All the bright optical lattices studied so far have been designed to obtain a circularly polarized light at the bottom of the optical potential wells. This condition minimizes the departure rate of the atoms from the fundamental adiabatic surface and permits an oscillating regime in a large range of parameters. We present here an experimental study of cesium atoms in a three-dimensional optical lattice, where the light is linearly polarized at the bottom of the potential wells. Temperature measurements and pump-probe spectroscopy give similar results for this lattice and for the conventional lin lin lattice (which have circular polarizations at the bottom of the wells) despite the fact that one lattice operates in the jumping regime and the other in the oscillating regime. We study the behaviour of the two types of lattices in a longitudinal magnetic field, with particular emphasis on the zero field and strong field regimes. The strong field situation is very simple because the eigenstates are then almost pure Zeeman substates and the adiabatic and diabatic potential surfaces are identical. The comparison between the zero-field and the high-field situations shows that the diabatic potentials are more appropriate to account for experimental observations in the novel lattice. Received: 9 October 1997 / Accepted: 6 November 1997     

Doppler-free spectroscopy of neon atoms dressed by optical photons in nearly-degenerate four-wave mixing

We have investigated nearly degenerate four-wave mixing in neon on the 607 nm line. We have considered the case where one pump beam saturates the medium while the two other incident beams have a much weaker intensity. The frequency of the most intense pump beam is equal to the frequency of the probe beam. When the frequency of the second pump beam is scanned, narrow resonances are observed. These resonances correspond to transitions between the energy levels of the atom dressed by the photons of the intense pump beam.     

Mode-coupling effects in simple fluids measured by neutron scattering

Summary After a summary of the relevant results from mode-coupling theory a review is given of the neutron scattering experiments that have given direct evidence for the existence of mode-coupling effects in simple fluids. The problem of determining the velocity autocorrelation function from neutron data is discussed in connection with experimental data on liquid sodium and on high-density hydrogen. Paper presented at the workshop ?Highlights on Simple Liquids?, held in Turin at ISI on 1–3 May, 1989.