The excited multiplet states of (tetraphenylporphinato)zinc(II) (ZnTPP) coordinated by p-pyridyl nitronyl nitroxide (p-nitpy), ZnTPP-p-nitpy, and of ZnTPP coordinated by m-nitpy, ZnTPP-m-nitpy, were studied by time-resolved electron paramagnetic resonance (TREPR). The TREPR spectra observed at 20 K and 0.5 µs after laser excitation were assigned to the lowest excited doublet (D 1 ) and quartet (Q 1 ) states for both the para and meta complexes. The TREPR spectra of the Q 1 state with electron-spin polarization (ESP) were well simulated for the first time. From the spectral simulation, it was established in general that the ESP in the Q 1 state was interpreted by selective intersystem crossing (ISC), which was generated by spin-orbit coupling (SOC) between the excited doublet states and the eigenfunctions of the Q 1 state in zero magnetic field. The TREPR spectra of the ZnTPP-nitpy systems were interpreted by selective ISC to the |( 1 / 2 〉 spin sublevels of the Q 1 state, which originated from SOC due to the zinc ion. The ESP in the D 1 state was interpreted by the difference between the internal conversion rate to the |+ 1 / 2 〉 spin sublevel and that to the |-1 / 2 〉 spin sublevel.
An electrodeposition technique was employed to synthesize CdS and SnS thin films. The optical and photoelectrochemical properties of these films were studied. Red emission peaks of as-deposited CdS thin films were observed around 650—700 nm at 77 K. Anodic photocurrents were observed for the CdS thin films used as semiconductor electrodes. Lowering current densities for the deposition increased both the photoluminescence intensity and the photocurrents. SnS thin films were prepared by a pulsed electrodeposition technique. The films had a large absorption coefficient of 105 cm−1 order. Stirring the electrolyte solution had a drastic effect on the film growth. This suggests that the diffusion of elemental sulfur which reacts with electrochemically formed Sn is the rate determining step of the SnS formation.
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