Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes. Part 15: The IR characteristics of phthalocyanine in homoleptic tetrakis(phthalocyaninato) rare earth(III)-cadmium(II) quadruple-deckers |
| |
| Affiliation: | 1. Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China;2. Key Laboratory of Functional Inorganic Materials Chemistry, Heilongjiang University, Ministry of Education, Harbin 150080, China;1. LPICM, Ecole Polytechnique, CNRS, 91128 Palaiseau, France;2. Department of Electrical Engineering, Columbia University, New York, NY 10027, USA;1. G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Akademicheskaya, 1, 153045 Ivanovo, Russia;2. Research Institute of Macroheterocycles of Ivanovo State University of Chemistry and Technology, 153000 Ivanovo, Russia |
| |
| Abstract: | The infra-red (IR) spectroscopic data for a series of twelve sandwich-type homoleptic tetrakis[2,3,9,10,16,17,23,24-octa(octyloxy)phthalocyaninato] rare earth(III)-cadmium(II) quadruple-decker complexes [Pc(OC8H17)8]M[Pc(OC8H17)8]Cd[Pc(OC8H17)8]M[Pc(OC8H17)8] (M = Y, Pr–Yb except Pm) have been collected with resolution of 2 cm−1 and their interpretation in terms tried by analogy with the IR characteristics of bis(phthalocyaninato) cerium double-decker [Pc(OC8H17)8]Ce[Pc(OC8H17)8] in which the macrocyclic ligands exist as the phthalocyanine dianion. Similar to the bis/tris(phthalocyaninato) rare earth sandwich counterparts, all the absorptions contributed primarily by or at least containing contribution from the vibrations of pyrrole or isoindole stretching, breathing or deformation or aza stretching in the IR spectra of these quadruple-decker compounds show dependent nature on the rare earth ionic size. The shift toward higher energy direction in the frequencies of these vibrations along with the decrease of the rare earth radii reveals the effective and increasing π–π interactions in these quadruple-decker sandwich compounds in the same order. Nevertheless, the decreased sensitivity of the frequencies of the above mentioned vibration modes in particular the weak absorption band due to the isoindole stretching at 1414–1416 cm−1 for the quadruple-decker on rare earth metal size in comparison with corresponding band for bis(phthalocyaninato) rare earth counterparts indicates the relatively weaker π–π interaction in these quadruple-deckers than in the double-deckers. |
| |
| Keywords: | Phthalocyanine Homoleptic quadruple-decker Infra-red spectroscopy Rare earth Sandwich complex |
| 本文献已被 ScienceDirect 等数据库收录！ |
|
