Synthesis and Diels–Alder Reactions of Some New (Phthalocyanine)nickel Complexes

Abstract

The octasubstituted (phthalocyanine)nickel complexes 4a,b, soluble in common organic solvents, bearing four dienophilic functionalities were synthesized from the corresponding phthalodinitriles 3a,b and nickel(II) acetate. Reaction of 4a with tetracyclone 5 led to the phthalocyanine–tetracyclone adduct 6 which is a precursor for an intermediate phthalocyanine 7 containing four isobenzofuran moieties. The capability of 7 to react as tetrakis(diene) was demonstrated by its reaction with naphthoquinone. Furthermore, the unsymmetrical phthalocyanines 13 and 16a,b,c containing one dienophilic functionality were synthesized using a statistical approach. Their tetracyclone adducts 17, 18a,b,c can be used for the synthesis of ladder‐type phthalocyanine dimers. The dimer 22 was synthesized from 18c and p‐benzoquinone via the isobenzofuran intermediate 19 and the benzoquinone adduct 21. For dehydration experiments the naphthoquinone monoadduct 23 was synthesized from 18c. Dehydration of 22 and 23 was carried out successfully with p‐toluenesulfonic acid. The Diels–Alder reactions are discussed with respect to the occurring exo/endo ratio.

A comparative study of the photophysical and phototoxic properties of octakis(decyloxy)phthalocyaninato zinc(II), incorporated in a hydrophilic polymer, in liposomes and in non-ionic micelles

“…This compound was readily prepared by the cyclotetramerisation of 1,2-dicyano-4,5-didecyloxybenzene, synthesised by a method similar to that described in the literature. [14][15][16] A mixture of 1,2-dicyano-4,5-didecyloxybenzene (91 mg, 2 × 10 Ϫ4 mol) and 90 mg of powdered zinc was heated at 210 ЊC in a closed vessel for 6.5 h. After cooling, methylene chloride (60 mL) was added and the remaining zinc filtered out under suction. The methylene chloride solution was evaporated in vacuo, leaving a green residue.…”

Comparative photophysical investigation of oxygen and sulfur as covalent linkers on octaalkylamino substituted zinc(ii) phthalocyanines

“…Since phthalocyanines are highly insoluble, many efforts were made to prepare lipophilic compounds through the introduction of peripheral alkyl chains. [31][32][33][34] In addition, phthalocyanine amphiphilicity was improved by employing sulfonated zinc(II) 6, 35 and aluminum phthalocyanines. 36,37 Also, zinc(II) phthalocyanines with peripheral substituents such as hydroxy and alkylhydroxy, 38,39 alkylamino 40- 42 and quaternary alkyl ammonium salts [43][44][45] have been synthesized.…”

A synthetic approach towards novel octa-substituted zinc(II) phthalocyanines with different solubility and photophysical properties

“…Since phthalocyanines are highly insoluble, many efforts were made to prepare lipophilic compounds through the introduction of peripheral alkyl chains [4][5][6][7]. In addition, phthalocyanine amphiphilicity was improved by employing sulfonated zinc(II) [2,8] and sulfonated aluminium phthalocyanines [9,10].…”