28888-81-5Relevant articles and documents
Planar and sandwich-type Pr(III) and Nd(III) chlorinated phthalocyaninates: Synthesis, thermal stability and optical properties
Kuzmina, Elena A.,Dubinina, Tatiana V.,Borisova, Nataliya E.,Tarasevich, Boris N.,Krasovskii, Vitaly I.,Feofanov, Ivan N.,Dzuban, Alexander V.,Tomilova, Larisa G.
, (2020)
A direct synthetic approach to four single-decker and one double-decker novel Pr(III) and Nd(III) complexes with 2,3,9,10,16,17,23,24-octachlorophthalocyaninate and 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecachlorophthalocyaninate has been developed. Synthesis of hexadeca-Cl-substituted Nd(III) bisphthalocyaninate has been carried out utilizing two preformed synthetic blocks: Nd(III) octachlorophthalocyaninate acetate and octachlorophthalocyanine ligand. Due to the electron withdrawing effect of 16 chlorine groups, this Nd(III) bisphthalocyaninate was obtained as a redox stable anionic form. Upfield lanthanide-induced shifts of the aromatic proton signals (up to 2.04 ppm for Pr(III) octachlorophthalocyaninate acetate) were observed in the 1H NMR spectra of the obtained phthalocyaninates. Thermal stability of the lanthanide (III) complexes was examined using thermogravimetric analysis combined with mass-spectrometry. The double-decker compound was shown to possess an increased thermal stability in comparison with the single-deckers up to ~400 °C. Linear and nonlinear optical properties of the Cl-substituted Nd(III) and Pr(III) phthalocyaninates have been investigated using z-scan technique. The best nonlinear optical response with the highest excited state absorption cross-section (σ1 = 1.1 × 10?15 cm?2) was found for the hexadeca-Cl-substituted Nd(III) monophthalocyaninate.
MANGANESE (III) CATALYZED C--H AMINATIONS
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Paragraph 0111; 0118-0122, (2019/04/25)
Reactions that directly install nitrogen into C—H bonds of complex molecules are significant because of their potential to change the chemical and biological properties of a given compound. Selective intramolecular C—H amination reactions that achieve high levels of reactivity, while maintaining excellent site-selectivity and functional-group tolerance is a challenging problem. Herein is reported a manganese perchlorophthalocyanine catalyst [MnIII(ClPc)] for intermolecular benzylic C—H amination of bioactive molecules and natural products that proceeds with unprecedented levels of reactivity and site-selectivity. In the presence of Br?nsted or Lewis acid, the [MnIII(ClPc)]-catalyzed C—H amination demonstrates unique tolerance for tertiary amine, pyridine and benzimidazole functionalities. Mechanistic studies indicate that C—H amination proceeds through an electrophilic metallonitrene intermediate via a stepwise pathway where C—H cleavage is the rate-determining step of the reaction. Collectively these mechanistic features contrast previous base-metal catalyzed C—H aminations.
Novel Synthesis of Metal-Free Phthalocyanines from Phthalimides and Phthalic Anhydrides with Hexamethyldisilazane
Uchida, Hitoshi,Yoshiyama, Hideyuki,Reddy, Paidi Yella,Nakamura, Shuichi,Toru, Takeshi
, p. 2083 - 2085 (2007/10/03)
Metal-free phthalocyanines and their peripherally substituted derivatives have been synthesized from unsubstituted and substituted phthalimides, phthalic anhydrides, and naphthalimide on heating with hexamethyldisilazane under mild conditions.
