Coherent effects in energy transport in model dendritic structures investigated by ultrafast fluorescence anisotropy spectroscopy

Measurements of ultrafast fluorescence anisotropy decay in model branched dendritic molecules of different symmetry are reported. These molecules contain the fundamental branching center units of larger dendrimer macromolecules with either three (C(3))- or four (T(d), tetrahedral)-fold symmetry. The anisotropy for a tetrahedral system is found to decay on a subpicosecond time scale (880 fs). This decay can be qualitatively explained by F?rster-type incoherent energy migration between chromophores. Alternatively, for a nitrogen-centered trimer system, the fluorescence anisotropy decay time (35 fs) is found to be much shorter than that of the tetramers, and the decay cannot be attributed to an incoherent hopping mechanism. In this case, a coherent interchromophore energy transport mechanism should be considered. The mechanism of the ultrafast energy migration process in the branched systems is interpreted by use of a phenomenological quantum mechanical model, which examines the two extreme cases of incoherent and coherent interactions.     

Synthesis of highly substituted meso-tetraarylporphyrins

meso-Tetraphenylporphyrin (and its derivatives), in the reaction with fuming yellow nitric acid (d=1.53), form either 5-(4-nitroaryl)-10,15,20-triarylporphyrin, 5,10-bis(4-nitroaryl)-15,20-diarylporphyrin, or 5,10,15-tris(4-nitroaryl)-20-arylporphyrin, depending on the reaction temperature (0-20 °C), amounts of the acid used, and reaction time. The above nitroporphyrins react, in the presence of a base (t-BuOK) at 0 °C, with carbanions (which bear nucleophugal groups at the carbanionic center: ⁻CH(Cl)SO₂Tol, ⁻CH(Br)SO₂Tol, and ⁻CH(Cl)SO₂NMe₂), leading to the nucleophilic substitution of hydrogen in one or more of the meso-nitroaryl rings. By this route, the preparation of the highly substituted ‘synthetic’ porphyrins (bearing up to ten O-, N-, Cl-, or C-substituents) was demonstrated.     

Nucleophilic substitution of hydrogen in meso-nitroaryl-substituted porphyrins—unprotected at the NH-centers in the core ring

Unprotected 5-(4-nitrophenyl)-10,15,20-triphenylporphyrin and 5,10-bis(4-nitrophenyl)-15,20-diphenylporphyrin react in the presence of a base at low temperature with carbanions (which bear a leaving group X at the carbanionic center) affording vicarious nucleophilic substitution of hydrogen (VNS) products in good yields (50-89%). The reactivity is explained in terms of the predominance of the porphyrin N-anion resonance forms at this temperature.     

Multinuclear magnetic resonance studies of 2‐aryl‐1,3,4‐selenadiazoles

2‐Aryl‐1,3,4‐selenadiazoles were studied by ¹H, ¹³C, ¹⁵N and ⁷⁷Se NMR spectroscopy. The results (chemical shifts and coupling constants) were correlated with Hammett substituent parameters as well as calculated chemical shifts and bond lengths. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of material selection and background impurity on interface property and resulted CIP-GMR performance

In this paper, we investigated the effect of background base pressure, wafer-transferring time between process modules, and stack layer material selection on the current-in-plane giant magneto-resistive (CIP-GMR) interface properties and the resulted CIP-GMR performance. Experimental results showed that seed layer/AFM interface, AFM/pinned layer (PL) interface, pinned layer/Ru interface, and reference layer (RL)/Cu spacer interface are among the most critical ones for a CIP-GMR device. By reducing the background impurity level (water moisture and oxygen), optimizing the wafer process flow sequence, and careful stack-layer material selection, such critical interfaces in a CIP-GMR device can be preserved. Consequently, a much robust GMR performance control can be achieved.