Optically tailored access to metastable electronic states

On irradiating a molecular system with a laser beam of ultraviolet or visible frequency, photon absorption occurs when an electronic state is at a suitable energy level relative to an initial state. Despite meeting this criterion, interesting metastable states can remain inaccessible because of symmetry constraints. In this Letter a mechanism, based on the input of an off-resonant beam, is shown to enable the population of such states. This is achievable because the laser-modified process involves different selection rules compared to conventional photon absorption. The effects of applying the stimulus beam to either a one- or two-photon process are examined

Bound and free waves in non-collinear second harmonic generation

We analyze the relationship between the bound and the free waves in the noncollinear SHG scheme, along with the vectorial conservation law for the different components arising when there are two pump beams impinging on the sample with two different incidence angles. The generated power is systematically investigated, by varying the polarization state of both fundamental beams, while absorption is included via the Herman and Hayden correction terms. The theoretical simulations, obtained for samples which are some coherence length thick show that the resulting polarization mapping is an useful tool to put in evidence the interference between bound and free waves, as well as the effect of absorption on the interference patternComment: 10 pages, 7 figure. to be published on Optics Expres

Ruthenacycles and Iridacycles as Catalysts for Asymmetric Transfer Hydrogenation and Racemisation

Ruthenacycles, which are easily prepared in a single step by reaction between enantiopure aromatic amines and [Ru(arene)Cl2]2 in the presence of NaOH and KPF6, are very good asymmetric transfer hydrogenation catalysts. A range of aromatic ketones were reduced using isopropanol in good yields with ee’s up to 98%. Iridacycles, which are prepared in similar fashion from [IrCp*Cl2]2 are excellent catalysts for the racemisation of secondary alcohols and chlorohydrins at room temperature. This allowed the development of a new dynamic kinetic resolution of chlorohydrins to the enantiopure epoxides in up to 90% yield and 98% enantiomeric excess (ee) using a mutant of the enzyme Haloalcohol dehalogenase C and an iridacycle as racemisation catalyst.

On the conveyance of angular momentum in electronic energy transfer

When electronic excitation transfer occurs, it is of considerable interest to establish whether angular momentum can also be conveyed in the process. The question is prompted by a consideration that when the participating chromophores are atoms, ions, or molecular systems having high local symmetry, the electronic excited states that are involved are generally characterized not only by energy, but by angular momentum properties. Moreover, it is known that electron spin can be communicated between quantum dot exciton states. Resolving the general issue entails an electrodynamic representation exploiting irreducible tensor methods, the analysis being illustrated by application to energy transfer associated with a variety of multipolar transitions. The results exhibit novel connections between an angular momentum content of the electromagnetic coupling and a strongly varying distance dependence. It is concluded that the communication of angular momentum does not in general map unambiguously between a donor and energy acceptor

The kinetics and mechanism of the organo-iridium catalysed racemisation of amines

The dimeric iodo-iridium complex [IrCp*I2 ]2 (Cp*=pentamethylcyclopentadiene) is an efficient catalyst for the racemisation of secondary and tertiary amines at ambient and higher temperatures with a low catalyst loading. The racemisation occurs with pseudo-first-order kinetics and the orresponding four rate constants were obtained by monitoring the time dependence of the concentrations of the (R) and (S) enantiomers starting with either pure (R) or (S) and show a first-order dependence on catalyst concentration. Low temperature 1H NMR data is consistent with the formation of a 1:1 complex with the amine coordinated to the iridium and with both iodide anions still bound to the metal-ion, but at the higher temperatures used for kinetic studies binding is weak and so no saturation zero-order kinetics are observed. A cross-over experiment with isotopically labelled amines demonstrates the intermediate formation of an imine which can dissociate from the iridium complex. Replacing the iodides in the catalyst by other ligands or having an amide substituent in Cp* results in a much less effective catalysts for the racemisation of amines. The rate constants for a deuterated amine yield a significant primary kinetic isotope effect kH/kD = 3.24 ndicating that hydride transfer is involved in the rate-limiting step

Enantiopure Ferrocene-Based Planar-Chiral Iridacycles:Stereospecific Control of Iridium-Centred Chirality

Reaction of [IrCp*Cl-2](2) with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6H4) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration S-p*,R-Ir*. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration S-c,S-p,R-Ir. Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate

Dispersion of the second-order nonlinear susceptibility in ZnTe, ZnSe, and ZnS

We have measured the absolute values of the second-harmonic generation (SHG) coefficient |d| for the zinc-blende II-VI semiconductors ZnTe, ZnSe, and ZnS at room temperature. The investigated spectral region of the fundamental radiation λF ranges from 520 to 1321 nm using various pulsed laser sources. In the transparent region of the II-VI semiconductors, the SHG coefficient exceeds the values of birefringent materials as ammonium dihydrogen phosphate (ADP) and potassium dihydrogen phosphate (KDP) by one or two orders of magnitudes. Above the E0 band gap a strong dispersion of |d| is observed, showing a maximum for a second-harmonic frequency close to the E1 gap. The experimental results are compared to calculated values using a simple three-band model including spin-orbit splitting. Substantial agreement is found to the experimentally observed dispersion of the second-order nonlinear susceptibility