Metalloporphyrins palladium porphyrinates

The use of metalloporphyrin-based materials for the detection of molecular oxygen is well developed. One approach that has been employed extensively involves the well-known phenomenon of quenching of metalloporphyrin phosphorescence by O2. Due to their high phosphorescence quantum yields and short triplet lifetimes, platinum and palladium porphyrins were originally suggested as probes... 

Fullerenes are spontaneously attracted to porphyrins and metalloporphyrins. The palladium-linked m-pyridyl dimer (shown in Figure 42) has a high binding constant in solution. Addition of C60 or C70 to solutions of these palladium-linked bis-porphyrins gave complexes that were chromatographically distinct from their individual components. This indication of tight binding was also seen in MALDI mass spectra.517... 

Abstract Pressure-sensitive paint (PSP) is applied to the areodynamics measurement. PSP is optical sensor based on the luminescence of dye probe molecules quenching by oxygen gas. Many PSPs are composed of probe dye molecules, such as polycyclic aromatic hydrocarbons (pyrene, pyrene derivative etc.), transition metal complexes (ruthenium(II), osumium(II), iridium(III) etc.), and metalloporphyrins (platinum (II), palladium(II), etc.) immobilized in oxygen permeable polymer (silicone, polystyrene, fluorinated polymer, cellulose derivative, etc.) film. Dye probe molecules adsorbed layer based PSPs such as pyrene derivative and porphyrins directly adsorbed onto anodic oxidised aluminium plat substrate also developed. In this section the properties of various oxygen permeable polymer for matrix and various dye probes for PSP are described. 

When porphyrins with much higher triplet energies such as palladium octaethylporphyrin (17 Et = 44.8 kcal mol" ) were used as sensitizers, even the cis trans isomerization of stilbene took place as a quantum chain process = 1-6) [95]. The high quantum efficiencies were explained by a quantum chain process in which the metalloporphyrin serves as both an energy donor and an acceptor. Since the quantum yield of cis trans isomerization of 1,2-diphenylpropene = 0-37) remained as a normal value under the same experimental conditions as those of stilbene, the potential energy surface of the triplet state is an important factor for occurrence of the quantum chain cis-trans isomerization. That is, in 1,2-diphenylpropene the triplet state exists exclusively as a perpendicular conformation, where the triplet state and the ground state lay very close in energy and the deactivation can only take place thermally. 

Various trifluoromethylated metalloporphyrins 54 were prepared in high yields by the reaction of brominated metalloporphyrins 53 (copper and nickel complexes) with stoichiometric amounts of FS02CF2C00Me/CuI in the presence of catalytic amounts of a palladium catalyst [28]. Similarly, the (CF3)2Cd-CF3CdBr-CuBr system was used as a source of trifluoromethyl anion in the synthesis of some porphyrin derivatives [29]. 

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