Time-resolved EPR and ODMR studies on the lowest excited triplet states of α-silyl and α-germyl ketones

Sublevel properties of the lowest excited triplet (T¹) nπ* states of α-silyl and α-germyl ketones were examined by means of ODMR, time-resolved EPR and optical spectroscopy. The EPR parameters, D, E and g, population ratios, and triplet lifetimes were obtained. The D value and the triplet lifetime varied among the molecules. In contrast the E value and population ratio remains nearly the same. These properties together with their solvent dependence and emission properties are interpreted in terms of spin-orbit couplings between T₁ (nπ*) and higher S₁ (nπ*), T₂ (ππ*) and S₂ (ππ*) states. An origin of the remarkable red-shifts of ^1,3 (π*) are discussed based on a model of delocalized n, π and π* electrons over the Si and Ge atoms. This model is also consistent with all the triplet properties obtained.     

A quantitative analysis of recombination data in high magnetic fields

Magnetic field effects on the hydrogen abstraction reaction of 4-methoxybenzophenone with thiophenol in several solvents of different viscosity have been reported, and the observed magnetic field dependence was explained as caused by the Δg and a polarized initial triplet radical pair state. The present work reports a quantitative analysis of the data based on a recently derived general analytical formula. It is found that the observed magnetic field dependence can be explained as originating from an unpolarized triplet state, if both the coherent mixing caused by different g values of the two radicals and the incoherent mixing due to spin relaxation are included. Several different expressions for the magnetic field dependence of the longitudinal and transverse relaxation rates were applied. Rather surprisingly, the different models gave almost identical fits. However, the values obtained of the microscopic parameters depended significantly on the model. Physically sensible parameter values were obtained only when the complete magnetic field dependence of the two relaxation times were used. For this model it was found that both the anisotropy factor of the g tensors and the diffusion coefficient agreed with expectations.     

Electric Field Enhancement of Nano Gap of Silver Prisms

Using numerical calculation, we examine the effects of gap distance of a pair of nano gap silver prisms with rounded corners on the local light intensity enhancement. Two peaks due to localized surface plasmon （LSP） excitation are observed in a wavelength range from 900nm to 300nm. The results demonstrate that peaks at a longer and a shorter wavelength corresponded to dipole-like and quadrupole-like LSP resonances, respectively. It is found that a gap distance up to 20 nm provides larger light intensity enhancement than that of a single silver nano prism with rounded corners. Furthermore, nano gap silver prisms are fabricated by direct focused ion beam processing, and we measure the scattering light spectrum of a pair of nano prisms by a confocal optical system. However, the two LSP peaks are not observed in visible range because the sizes of the nano gap and prisms are too large.     

Magnetic field effects on the hydrogen abstraction reaction of triplet 4-methoxybenzophenone with thiophenol as studied by a picosecond laser flash photolysis technique

The hydrogen abstraction reaction of triplet 4-methoxybenzophenone with thiophenol at 265 K has been studied with a newly developed picosecond laser flash photolysis apparatus under magnetic fields of 0–1.7 T. The decay rate constant of the radical pair generated was found to increase from 3.42 × 10⁹ s^?1 to 4.15 × 10⁹ s^?1 with increasing the magnetic field from 0 to 1.7 T. The observed magnetic field effects can be explained by the Δg mechanism. Using the simple kinetics model with the Δg mechanism, the rate constant of the escape process from the pair (k _esc) and two rate constants for the T-S spin conversion process (k _T-S) at 0 and 1.7 T were found to be 1.97 × 10⁹ s^?1, 1.45 × 10⁹ s^?1, and 2.12 × 10⁹ s^?1, respectively. From the magnetic field dependence on k _T-S, the difference in the g values of the 4-methoxybenzophenone ketyl and phenylthiyl radicals was estimated to be 0.0087.     

Re-examination of the magnetic field effects on the thermal reactions of benzyl and pentafluorobenzyl halides with n-butyllithium in hexane

The magnetic field effects reported in 1973 for the thermal reaction of benzyl and pentafluorobenzyl chlorides with n-butyllithium in hexane have been re-examined under various reaction conditions. Using a new reaction apparatus, which has an electromagnet (up to 1.49 T) in a glove box under an argon atmosphere (H₂O and O₂ < 1 ppm), a study has been made on the effects on the yields of asymmetrical products (phenylpentane and pentafluorophenylpentane) and symmetrical ones (diphenylethane and decafluorodiphenylethane) in the absence and presence of external magnetic fields. No appreciable magnetic field effects have been observed with change of sample concentration, reaction temperature, or magnetic field strength, or with various benzyl halides.