Infrared Spectra of Phthalocyanine and Naphthalocyanine in Sandwich-Type (Na) phthalocyaninato and Porphyrinato Rare-Earth Complexes.II.~* The Effects of Rare-Earth Ionic Size on the IR Characteristics of Naphthalocyanine in Bis (naphthalocyaninato)

摘要

The infra-red (IR) spectroscopic data for a series of 28 homoleptic substituted bis (naphthalocyaninato) rare-earth complexes M(2,3-Nc~*)_2 [M = Y, La-Lu except Pm; H_2Nc~* = 3(4),12(13),21(22),30(31)-tetra (tert-butyl)-2,3-naphthalocyanine (H_2TBNc) and 3,4,12,13,21,22,30,31-octa(dodecylthio)-2,3-naphthalocyanine (H_2ODTNc)] have been collectedw ith a resolution of 2 cm~(-1). These neutral sandwich complexes are radicals due to their composition (Nc~*)~(2-)M~(III)(Nc~*)~-, wherein the unpaired electron is delocalized over both macrocycles on the vibrational time scale. Compared to spectra obtained with low resolution, such as 4 cm~(-1), a larger number of vibrational modes could be distinguished. The IR spectra for M(ODTNc)_2 are much simpler than those of M(TBNc)_2, revealing de distinguished. The IR spectra for M(ODTNc)_2 are much simpler than those of M(TBNc)_2, revealing the relatively higehr symmetry of the former molecules. By analogy with bis (phthalocyaninato) rare-earth counterparts, the pyrrole stretching absorptions at 1314-1317 and 1323-1330 cm~(-1) for M(TBNc)_2 and at 1316-1327 cm~(-1) for M(ODTNc)_2 are assigned to the IR market bands of the assigned to C-H wagging, 1350-1355 cm~(-1) attributed to pyrrole stretchings, and 1389-1394 cm~(-1) due to naphthalene stretchings, have been found to shift slightly to higher energy along with the rare-earth contraction, clearly demonstrating the effect of rare-earth ionic radius.