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Towards Clarifying the Role of O 2 during the Phthalocyanine Synthesis
Author(s) -
Wang Kang,
Pan Houhe,
Jiang Jianzhuang
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201504050
Subject(s) - phthalonitrile , chemistry , phthalocyanine , isoindole , lutetium , chromophore , solvent , ligand (biochemistry) , polymer chemistry , photochemistry , medicinal chemistry , organic chemistry , oxide , biochemistry , receptor , yttrium
The role of O 2 within the synthesis of phthalocyanines (Pcs) has remained unclear in the past century. Here, we demonstrate that O 2 , in cooperation with the solvent n ‐pentanol, participates in the cyclic tetramerization of phthalonitriles over the half‐sandwich complex template [Lu(Pc)(acac)] (acac=acetylacetonate) and terminates the reaction at the stage of uncyclized isoindole oligomeric derivatives rather than the phthalocyanine chromophores, resulting in the isolation of the heteroleptic (phthalocyaninato)(triisoindole‐1‐one) lutetium double‐decker complexes [(Pc)Lu(TIO‐I)] (TIO‐I=3,4,7,8,11,12‐sexi(2,6‐diisopropylphenoxy)‐15‐[4,5‐di(2,6‐diisopropylphenoxy)‐2‐cyanobenzimidamido]triisoindole‐1‐one) and [(Pc)Lu(TIO‐II)] (TIO‐II=3,4,7,8,11,12‐sexi(2,6‐dimethylphenoxy)‐15‐[4,5‐di(2,6‐dimethylphenoxy)‐2‐cyanobenzimidamido]triisoindole‐1‐one) with the help of bulky substituents at the phthalonitrile periphery and an unsubstituted phthalocyanine ligand in the double‐decker skeleton. Nevertheless, the cyclic tetramerization of the phthalonitriles was revealed to be sensitive to O 2 with the reaction progression also depending on the oxygen concentration/content, leading to the O 2 ‐senstive and ‐dependent nature for the isolation of phthalocyanine derivatives.