title: Towards Clarifying the Role of O2 during the Phthalocyanine Synthesis.
abstract: The role of O2 within the synthesis of phthalocyanines (Pcs) has remained unclear in the past century. Here, we demonstrate that O2 , 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 O2 with the reaction progression also depending on the oxygen concentration/content, leading to the O2 -senstive and -dependent nature for the isolation of phthalocyanine derivatives.
authors.affiliation: Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing 100083 (P. R. China).
authors.forename: Kang
authors.initials: K
authors.lastname: Wang
authors.affiliation: Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing 100083 (P. R. China).
authors.forename: Houhe
authors.initials: H
authors.lastname: Pan
authors.affiliation: Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing 100083 (P. R. China). jianzhuang@ustb.edu.cn.
authors.forename: Jianzhuang
authors.initials: J
authors.lastname: Jiang
keywords: isoindole oligomers; lutetium; oxygen; phthalocyanines