TY - JOUR
T1 - (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
AU - Sheng, Ning
AU - Zhang, Yuexing
AU - Xu, Hui
AU - Bao, Meng
AU - Sun, Xuan
AU - Jiang, Jianzhuang
PY - 2007
Y1 - 2007
N2 - 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.
AB - 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.
KW - Crown ether
KW - Molecular symmetry
KW - Phthalocyanines
KW - Supramolecular chemistry
UR - http://www.scopus.com/inward/record.url?scp=34547284275&partnerID=8YFLogxK
U2 - 10.1002/ejic.200700148
DO - 10.1002/ejic.200700148
M3 - Article
AN - SCOPUS:34547284275
SN - 1434-1948
SP - 3268
EP - 3275
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 20
ER -