title: Nonperipheral Tetrakis(dibutylamino)phthalocyanines. New Types of 1,8,15,22-Tetrakis(substituted)phthalocyanine Isomers.
abstract: Cyclic tetramerization of 3-(dibutylamino)phthalonitrile in refluxing n-pentanol in the presence of magnesium pentanoate afforded the four regioisomer-containing nonperipheral 1,8-/11,15-/18,22-/25-tetrakis(dibutylamino)phthalocyaninato magnesium complexes with the 1,8,15,22-tetrakis(dibutylamino)phthalocyanine isomer Mg{Pc[α-N(C4H9)2]4-C4} (2). This, in combination with its much superior crystallinity over the remaining three isomers, renders the easy isolation of 2 only through two simple recrystallizations from THF and methanol. Treatment of 2 with trifluoroacetic acid induced the isolation of metal-free 1,8,15,22-tetrakis(dibutylamino)phthalocyanine, H2{Pc[α-N(C4H9)2]4-C4} (1), which further reacted with M(OAc)2·nH2O (M = Ni, Zn) in refluxing n-pentanol, giving the 1,8,15,22-tetrakis(dibutylamino)phthalocyaninato metal complexes M{Pc[α-N(C4H9)2]4-C4} (M = Ni (3), Zn (4)). The full series of four 1,8,15,22-tetrakis(dibutylamino)phthalocyanine isomeric compounds have been characterized by a series of spectroscopic methods and single-crystal X-ray diffraction analyses. Obviously, the present result provides a simple and effective pathway for the synthesis and isolation of novel 1,8,15,22-tetrakis(dibutylamino)phthalocyanine isomeric derivatives, providing one step forward toward completing bis(alkyl)amino-incorporated phthalocyanine species.
authors: Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing , Beijing 100083, People's Republic of China.
authors: Yuxiang
authors: Y
authors: Chen
authors: State Key Laboratory of Crystal Materials, Shandong University , Jinan 250012, People's Republic of China.
authors: Wenjuan
authors: W
authors: Fang
authors: Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing , Beijing 100083, People's Republic of China.
authors: Kang
authors: K
authors: Wang
authors: State Key Laboratory of Crystal Materials, Shandong University , Jinan 250012, People's Republic of China.
authors: Wei
authors: W
authors: Liu
authors: Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing , Beijing 100083, People's Republic of China.
authors: Jianzhuang
authors: J
authors: Jiang