TY - JOUR
T1 - Synthetic, structural, spectroscopic, and electrochemical studies, of heteroleptic tris(phthalocyaninato) rare earth complexes
AU - Bian, Yongzhong
AU - Li, Lei
AU - Wang, Daqi
AU - Choi, Chi Fung
AU - Cheng, Diana Y.Y.
AU - Zhu, Pehua
AU - Li, Renjie
AU - Dou, Jianmin
AU - Wang, Rongming
AU - Pan, Na
AU - Ng, Dennis K.P.
AU - Kobayashi, Nagao
AU - Jiang, Jianzhuang
PY - 2005/7/4
Y1 - 2005/7/4
N2 - Three heteroleptic tris(phthalocyaninato) rare-earth triple-decker complexes [(Pc)M(Pc)M{Pc(α-OC5H11)4}] [M = Sm, Gd, Lu; Pc = phthalocyaninate; Pc(α-OC5H 11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninate] have been prepared as racemic mixtures by treating [M{Pc(α-OC 5H11)4}(acac)], generated in situ, with the bis(phthalocyaninato) rare-earth double-decker complex [M(Pc)2] in refluxing n-octanol. The molecular structures of the gadolinium and lutetium complexes have been determined by single-crystal X-ray diffraction analysis, both of which adopt the asymmetrical structure [(Pc)M(Pc)M{Pc(α-OC 5H11)4}]. The outer Pc and Pc(α-OC 5H11)4 rings are significantly domed, while the inner Pc ring is essentially planar. The ring-to-ring separation between the two adjacent Pc rings, as defined by the two N4 mean planes, diminishes from [(Pc)Gd(Pc)Gd{Pc(α-OC5H11) 4}] to [(Pc)Lu(Pc)Lu{Pc(α-OC5H11) 4}] as a result of the smaller LuIII ion. The decreased molecular symmetry for these complexes has also been revealed by the NMR spectra of the samarium and lutetium analogs, in which four sets of signals appear for the inner Pc ring protons due to the special disposition of the neighboring Pc(α-OC5H11)4 ring. Electrochemical studies have revealed four one-electron oxidations and up to five one-electron reductions for these complexes. The dependence of the phthalocyanine Q band as well as the first and second oxidation potentials on the size of the metal center indicates that substantial π-π interactions are present in these compounds.
AB - Three heteroleptic tris(phthalocyaninato) rare-earth triple-decker complexes [(Pc)M(Pc)M{Pc(α-OC5H11)4}] [M = Sm, Gd, Lu; Pc = phthalocyaninate; Pc(α-OC5H 11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninate] have been prepared as racemic mixtures by treating [M{Pc(α-OC 5H11)4}(acac)], generated in situ, with the bis(phthalocyaninato) rare-earth double-decker complex [M(Pc)2] in refluxing n-octanol. The molecular structures of the gadolinium and lutetium complexes have been determined by single-crystal X-ray diffraction analysis, both of which adopt the asymmetrical structure [(Pc)M(Pc)M{Pc(α-OC 5H11)4}]. The outer Pc and Pc(α-OC 5H11)4 rings are significantly domed, while the inner Pc ring is essentially planar. The ring-to-ring separation between the two adjacent Pc rings, as defined by the two N4 mean planes, diminishes from [(Pc)Gd(Pc)Gd{Pc(α-OC5H11) 4}] to [(Pc)Lu(Pc)Lu{Pc(α-OC5H11) 4}] as a result of the smaller LuIII ion. The decreased molecular symmetry for these complexes has also been revealed by the NMR spectra of the samarium and lutetium analogs, in which four sets of signals appear for the inner Pc ring protons due to the special disposition of the neighboring Pc(α-OC5H11)4 ring. Electrochemical studies have revealed four one-electron oxidations and up to five one-electron reductions for these complexes. The dependence of the phthalocyanine Q band as well as the first and second oxidation potentials on the size of the metal center indicates that substantial π-π interactions are present in these compounds.
KW - Heteroleptic complexes
KW - Phthalocyanines
KW - Rare earths
KW - Sandwich complexes
KW - Triple-decker complexes
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U2 - 10.1002/ejic.200400920
DO - 10.1002/ejic.200400920
M3 - Article
AN - SCOPUS:22144483476
SP - 2612
EP - 2618
JO - Berichte der deutschen chemischen Gesellschaft
JF - Berichte der deutschen chemischen Gesellschaft
SN - 0365-9496
IS - 13
ER -