title: Raman spectroscopic characteristics of phthalocyanine in mixed [5-(4-hydroxyphenyl)-10,15,20-tris(4-octyloxyphenyl)porphyrinato]-(phthalocyaninato) rare earth triple-deckers.
abstract: Raman spectroscopic data in the range of 500-1,800 cm(-1) for a series of nine mixed rare earth triple-deckers M(2)[TO(OH)PP](Pc)(2) [M=La…Dy, except Pm; H(2)Por=5-(4-hydroxyphenyl)-10,15,20-tris(4-octyloxyphenyl)porphyrin] have been collected using laser excitation sources emitting at 632.8 nm. Comparison with the Raman spectra of the corresponding bis(phthalocyaninato) and mixed double-decker rare earths reveals that the Raman characteristics of these mixed triple-deckers M(2)(III)[TO(OH)PP](Pc)(2) are dominated by Pc(2-) contributions. There is no obvious band that can be assigned to the [TO(OH)PP](2-) moiety. Under excitation at 632.8 nm, typical Raman marker bands of the phthalocyanine dianions Pc(2-) were observed at 1514-1,526 cm(-1) as medium band, resulting from the coupling of pyrrole CC and aza CN stretchings. For Ce(2)(III-IV)[TO(OH)PP](Pc)(2), a strong band at 1,521 cm(-1) with contribution from both pyrrole CC and aza CN stretches as well as the isoindole stretches was the marker Raman band of Pc(2-). The Raman spectra of these mixed triple-decker complexes reveal that most of the Raman vibrations derived from pyrrole stretching, isoindole breathing, CH bend and aza stretching are decreased sensitive to the rare earth ionic size, and remain basically unchanged along with the lanthanide contraction. These facts indicate that the π-π interactions in these mixed triple-deckers are weaker than those in the double-deckers.
authors.affiliation: Department of Chemistry, School of Sciences, Tianjin University, Tianjin 300072, PR China.
authors.forename: Guihong
authors.initials: G
authors.lastname: Bao
authors.forename: Wendong
authors.initials: W
authors.lastname: Wang
authors.forename: Yajun
authors.initials: Y
authors.lastname: Mao
authors.forename: Fanli
authors.initials: F
authors.lastname: Lu
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D007211:Indoles / Q000737:chemistry*; D054833:Isoindoles; D008674:Metals, Rare Earth / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry*; D013059:Spectrum Analysis, Raman
chemical_list: D056831:Coordination Complexes; D007211:Indoles; D054833:Isoindoles; D008674:Metals, Rare Earth; D011166:Porphyrins; C013647:phthalocyanine