Aluminum complexes phthalocyanines

The key point of the high-speed living polymerization is the steric suppression of an undesired reaction between the nucleophilic growing species and the Lewis acid, for which not only the steric bulk of the Lewis acid but also that of the porphyrin ligand is considered important. The benefit of using a Lewis acid holds even for the aluminum complexes with phthalocyanine (11), tetraazaannulene (12), and. Schiff bases (13-15). As initiators, these complexes exhibit much lower activity for the polymerization of PO than aluminum porphyrin 1 (X=C1). 

Aluminum l,l -bi-2-naphthol complex phthalocyanine complexes Arsenic Hu96 Lez93... 

As already described, aluminum complexes of tetra-azaannulene (9) and phthalocyanine (10) have much lower reactivities than aluminum porphyrins for the polymerization of epoxides (11). However, in the presence of appropriate Lewis acids such as 44 or 45, the polymerizations with these initiators take place rapidly to give polyethers with fairly narrow MWD. ... 

The dramatic acceleration observed for the ROP of epoxides when (255) is present has also been observed with several other aluminum-based initiators, including salen- (325)-(327), tetraazaan-nulene- (328) and phthalocyanine- (329) ligated systems.946 For example, (325) polymerizes PO extremely slowly at room temperature (4% conversion of 50 equivalents over 8 days), but in the presence of MAD (255), 200 equivalents require just 70min to attain 43% con version.794,795,947 Complex (328) shows a similar increase in activity upon addition of MAD 200 equivalents PO reach 74% conversion within 90 seconds in the absence of MAD such a yield requires several days. 

There are other metal complexes, such as tin, aluminum, magnesium, iron, cobalt, titanium, and vanadium complexes, which are similarly useful in stabilizing a particular phthalocyanine modification. Moreover, carboxy, carbonamido, sulfo, or phosphono-copper phthalocyanine may be admixed during fine dispersion of the pigment. 

Aluminum porphyrins first came to attention with the discovery that the simple alkyl complex Al(TPP)Et was capable of activating CO2 under atmospheric pressure. Both irradiation with visible light and addition of 1-methylimidazole were required for the reaction, which was proposed to proceed by initial coordination of the base to aluminum. The aluminum porphyrin containing direct product of CO2 insertion was not isolated, but was proposed on the basis of IR data to be (TPP)A10C(0)Et, which was then treated with HCl gas, presumably liberating propanoic acid, subsequently isolated as the butyl or methyl ester after reaction with 1-butanol or diazomethane, respectively [Eq. (5)]. Insertion of CO2 into the Al—C bond of an ethylaluminum phthalocyanine complex has also been reported. ... 

Catalytic activity of the aluminum-Schiff base system is dramatically enhanced by adding a bulky Lewis acid (Table 2). Inoue et al. reported that a combination of 3 with 2c led to over 1000 times acceleration in the polymerization of PO at room temperature compared with the polymerization in the absence of 2c.The resulting polymers have narrow MWDs, molecular weights close to those estimated, assuming that every molecule of 3 forms one polymer chain. The same accelerating effect of 2c is also demonstrated in the polymerization of PO by using aluminum-phthalocyanine and aluminum-tetraazaannulene complexes, 4 and 5, which exhibit very low catalytic activities without 2c. 

The phosphorescent organic light emitting diodes (PHOLEDs) based on Ir(dmp>py)3 complexes were fabricated by the vacuum deposition technique with the following configuration ITO/copper phthalocyanine (CuPc, 10 nm) as hole injection layer/4,4 -bis[(l-naphthyl)(phenyl)-amino]-l,l -biphenyl (NPD, 40 nm) as hole transport layer/CBP Ir(dmppy)3 (8%) (20 nm) as emissive layer/2,9-dimethyl-4,7-diphenyl-l,10-phenanthroline (BCP, 10 nm) as a hole blocking layer/ tris-(8-hydroxyquinoline)aluminum (Alqs, 40 nm) as an electron transport layer/LiF (1 nm) as electron injection layer/ A1 (100... 

Thus (XX) reacts with phenol in pyridine to form diphenoxysilicon phthalocyanine (XXII), with benzyl alcohol to form (XXIII), and with triphenylsilanol to form (XXIV) (168,170, 200). These complexes sublime readily without decomposition (cf. corresponding aluminum derivatives). Bis(diphenylmethylsiloxy)silicon phthalocyanine, which melts before subliming, is one of the very few metal phthalocyanines which actually melt (873). The siloxy complex (XXIV) may also be prepared in benzyl alcohol, thus implying that the Si—O—Si(Pc)—0—Si backbone is more stable than C—O—Si(Pc)—O—C. The dibenzyloxy derivative (XXIII) reacts with diphenylsilanediol to form bis(benzyloxydiphenylsiloxy)silicon phthalocyanine (XXV). 

Synthesis of phthalocyanine-2,9,16,23-tetrasulfonic acid aluminum(III) complex 48 (R = -SO3 , M == Al(OH)) 10.73 g (40 mmol) 4-sulfophthalic acid monosodium salt, 1.28 g (24 mmol) ammonium chloride, 24.02 g (400 mmol) urea and 0.185 g (0.15 mmol) ammonium molybdate (all chemicals dried) were intensively mixed and placed in a 250 mL glass vessel under dry inert gas. 2 g (15 mmol) water-free aluminum trichloride (purity 99.99%) was added under inert gas. The mixture was heated at first at 140 °C and then within 30 min with stirring to 190 °C, followed by heating at 210 °C for 24 h under inert gas. The blue-colored reaction product was pulverized, treated for 24 h with 1 M aqueous... 

TABLE 13.3 Emission Lifetime of the Singlet State of Phthalocyanine Complexes of Zinc and Aluminum... 

Cesar A. T. Laia, Silvia M. B. Costa, David Philhps. (2004). Electron-Transfer Kinetics in Sulfonated Aluminum Phthalocyanines/Cytochrome c Complexes. J. Phys. Chem., 7506-7514. 

N. S. Zefirov, Russ. Chem. Bull. Int. Ed. 2011, 60, 242-247. Sihca gel-immobiUzed aluminum phthalocyanine complex as a heterogeneous catalyst for the synthesis of a-amino phosphonates. 

Various metal complexes such as metal-phthalocyanines, metal-salenes or Ru-pyridyl complexes were incorporated in molecular sieves such as cavity-structured zeolites (faujasites, supercages with 1.3 nm diameter), channel-structured aluminum phosphates... 

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