Bis[1,4,8,11,15,18,22,25-octa(butyloxyl)phthalocyaninato] rare earth double-decker complexes: synthesis, spectroscopy, and molecular structure.
Homoleptic octa-alpha-substituted bis(phthalocyaninato) rare earth double-deckers HM(III)[Pc(alpha-OC(4)H(9))(8)](2) [M = Eu (1), Y (2); Pc(alpha-OC(4)H(9))(8) = 1,4,8,11,15,18,22,25-octa(butyloxyl)phthalocyanine] have been prepared by treating the metal-free phthalocyanine H(2)Pc(alpha-OC(4)H(9))(8) with the corresponding M(acac)(3).nH(2)O (acac = acetylacetonate) in the presence of organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and benzo-18-crown-6/benzo-15-crown-5 in refluxing n-octanol. To the best of our knowledge, it is the first example of homoleptic non-peripherally octa(alkoxyl)-substituted bis(phthalocyaninato) rare earth complexes. Comparative studies on a series of reactions reveal the key role of DBU as catalyst and crown ether as template in the formation of homoleptic rare earth double-decker complexes with structurally highly deformed non-peripherally octa(butyloxy)-substituted phthalocyanine ligand. The molecular structure of complex 1 has been determined by single-crystal X-ray diffraction analysis. The metal center is octa-coordinated by the isoindole nitrogen atoms of the two phthalocyaninato ligands, forming a distorted square antiprism. Despite the extremely non-planar saddle conformation employed by metal free H(2)Pc(alpha-OC(4)H(9))(8) molecule, both the phthalocyanine rings in HEu(III)[Pc(alpha-OC(4)H(9))(8)](2) (1) adopt a conformation that is domed toward the europium center, similar to corresponding unsubstituted or beta-substituted bis(phthalocyaninato) analogues. These two bis(phthalocyaninato) rare earth double-deckers have also been characterized by a wide range of spectroscopic methods including MS, (1)H NMR, UV-vis, IR, and EPR. Structural and spectroscopic studies reveal that the pi-pi interaction between the two Pc(alpha-OC(4)H(9))(8) rings is weaker than that for the corresponding unsubstituted or beta-substituted bis(phthalocyaninato) analogues.
Gao
Yingning
Y
Department of Chemistry, University of Science and Technology Beijing, Beijing, 100083, China.
Li
Renjie
R
Dong
Shuai
S
Bian
Yongzhong
Y
Jiang
Jianzhuang
J