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(Phthalocyaninato)copper(II) Complexes Fused with Different Numbers of 15‐Crown‐5 Moieties – Synthesis, Spectroscopy, Supramolecular Structures, and the Effects of Substituent Number and Molecular Symmetry
Author(s) -
Sheng Ning,
Zhang Yuexing,
Xu Hui,
Bao Meng,
Sun Xuan,
Jiang Jianzhuang
Publication year - 2007
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200700148
Subject(s) - chemistry , substituent , 15 crown 5 , supramolecular chemistry , crystallography , copper , ion , stereochemistry , crystal structure , crown ether , organic chemistry
Symmetrical (phthalocyaninato)copper(II) complexes Cu(Pc′) [Pc′ = Pc(15C5), Pc(opp‐15C5) 2 , Pc(adj‐15C5) 2 , Pc(15C5) 3 ; Pc = unsubstituted phthalocyaninate, Pc(15C5) = 2,3‐(15‐crown‐5)phthalocyaninate, Pc(opp‐15C5) 2 = 2,3,16,17‐bis(15‐crown‐5)phthalocyaninate, Pc(adj‐15C5) 2 = 2,3,9,10‐bis(15‐crown‐5)phthalocyaninate, Pc(15C5) 3 = 2,3,9,10,16,17‐tris(15‐crown‐5)phthalocyaninate] ( 2 – 5 ) have been prepared by the reaction of corresponding heteroleptic bis(phthalocyaninato)europium complexes Eu(Pc)(Pc′) [Pc′ = Pc(15C5), Pc(opp‐15C5) 2 , Pc(adj‐15C5) 2 , Pc(15C5) 3 , Pc(15C5) 4 ; Pc = unsubstituted phthalocyaninate] with Cu(OAc) 2 in dry dmf at 100 °C. For the purpose of comparative studies, the symmetrical counterparts CuPc ( 1 ) and CuPc(15C5) 4 [Pc(15C5) 4 =2,3,9,10,16,17,24,25‐tetrakis(15‐crown‐5)phthalocyaninate]( 7 ) have also been prepared. These monomeric complexes have been characterized by spectroscopic methods in addition to elemental analysis. Having a series of closely related phthalocyanines with a different number and/or disposition of 15‐crown‐5 groups at the peripheral positions, the effects of 15‐crown‐5 substituent number and molecular symmetry on the electronic absorption spectra, infra‐red (IR) spectra, and supramolecular structure formation induced by K + ions have been investigated. Systematic studies on the formation of dimeric supramolecular structures of the series of monomers 2 – 6 reveal and confirm the previously proposed two‐step three‐stage process of K + ‐induced dimerization of phthalocyanines with three or four 15‐crown‐5 moieties.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)