944934-37-6Relevant academic research and scientific papers
Preparation and optical properties of polyimide films linked with porphyrinato Pd (II) and Pt (II) complexes through a triazine ring and application toward oxygen sensors
Kimura, Takeshi,Watanabe, Shuichi,Sawada, Shin-Ichi,Shibasaki, Yuji,Oishi, Yoshiyuki
, p. 1086 - 1094 (2017)
5-(3-Aminophenyl)-10,15,20-tri(4-methylphenyl) porphyrinato Pd (II) and Pt (II) complexes (2a-Pd) and (2a-Pt), respectively, were prepared from 5-(3-nitrophenyl)-10,15,20-tri(4-methyl-phenyl)porphyrin via two-step reactions, and reacted with cyanuric chloride to produce corresponding porphyrin derivatives (3a-Pd) and (3a-Pt) with a dichlorotriazine ring. Aromatic polyimides were prepared using diamine (4); triazine dichlorides having porphyrin units (3a-Pd), (3a-Pt), (3c-Pd), and (3c-Pt); fluoro-functionality 6-(p-perfluorononenyl oxyanilino)triazine-2,4-dichloride (6); and tetracarboxylic dianhydride (5) in N-methyl-2-pyrrolidone (NMP) at an elevated temperature up to 300 °C. The resulting viscous polymeric solution was cast on a glass plate, affording well-proportioned reddish transparent films with number-average molecular weights of 25,000–38,000. Glass transition temperatures of the polymers were ～230 °C; the films were stable up to 400 °C in air. The film emission spectra showed a broad peak ～670 nm, similar to those of porphyrins (2a-Pd) and (2a-Pt) dispersed in a polystyrene matrix. While the luminescence of these polymer films was quenched with oxygen, it rapidly recovered under a deoxygenated atmosphere. The polyimide film sensitivity to oxygen was higher under low oxygen concentrations than those of porphyrins (2a-Pd) and (2a-Pt) dispersed in polystyrene.
Remote site photosubstitution in metalloporphyrin-rhenium tricarbonylbipyridine assemblies: Photo-reactions of molecules with very short lived excited states
Gabrielsson, Anders,Lindsay Smith, John R.,Perutz, Robin N.
experimental part, p. 4259 - 4269 (2009/02/03)
The synthesis is reported of a series of metalloporphyrins (and the corresponding free-base porphyrin), mono-meso-substituted with a bipyridyl group via an amide link at the 4-position of one phenyl group: [Re(CO) 3(Pic)Bpy-MTPP][OTf], where M = Mg, Zn, Pd or 2H, Pic = 3-picoline, Bpy = 2,2′-bipyridine, TPP = tetraphenylporphyrin. The photochemical reactions of the assemblies with the sacrificial electron donor triethylamine have been investigated by IR spectroscopy and compared to the behaviour of analogues of the type Bpy-MTPP without rhenium. Selective long-wavelength irradiation of the metalloporphyrin unit in the presence of excess picoline leads to reduction at the rhenium bipyridine centre. In the absence of 3-picoline, the latter is not reduced, but substituted by added halide or by the THF solvent. Mechanistic analysis highlights the differences between the zinc and magnesium chelate on the one hand and the palladium porphyrin on the other. The free-base assembly, [Re(CO)3(Pic)Bpy-H2TPP][OTf] is unreactive. The zinc and magnesium porphyrin assemblies initially coordinate Et3N before undergoing photo-induced inner-sphere electron transfer from the triethylamine to form a charge-shifted excited state of the assembly. In contrast, the palladium-based dyad reacts via outer-sphere reductive quenching of a porphyrin-based excited state. The substitution products are postulated to form by a mechanism involving an electron-transfer chain.
