(Table 1) Biostratigraphic datums of ODP Leg 133 sites

We use benthic foraminifers to reconstruct the Neogene paleobathymetric history of the Marion Plateau, Queensland Plateau, Townsville Trough, and Queensland Trough on the northeastern Australian margin (Ocean Drilling Program Leg 133). Western Queensland Plateau Site 811/825 (present depth, ~938 m) deepened from the neritic zone (0-200 m) to the upper bathyal zone (200-600 m) during the middle Miocene (~13-14 Ma), with further deepening into the middle bathyal zone (600-1000 m) occurring during the late Miocene (~7 Ma). A depth transect across the southern Queensland Plateau shows that deepening from the outer neritic zone (100-200 m) to the upper bathyal zone began during the latest Miocene (~6 Ma) at the deepest location (Site 813, present depth, 539.1 m), whereas the shallower Sites 812 and 814 (present depths, 461.6 and 520.4 m, respectively) deepened during the late Pliocene (~2.7 and ~2.9 Ma). At Marion Plateau Site 815 (present depth, 465.5 m), water depth increased during the late Miocene (~6.7 Ma) from the outer neritic to the upper bathyal zone. Nearby Site 816 (present water depth, 437.3 m) contains Pliocene upper bathyal assemblages that directly overlie middle Miocene shallow neritic deposits; the timing of the deepening is uncertain because of a late Miocene hiatus. On the northern slope of the Townsville Trough (Site 817, present depth, 1015.8 m), benthic foraminifers and sponge spicules indicate deepening from the lower upper bathyal (400-600 m) to the middle bathyal zone in the late Miocene (by ~6.8 Ma). Benthic foraminiferal faunas at nearby Site 818 (present water depth, 752.1 m) do not show evidence of paleobathymetric change; however, a late Pliocene (~2-3 Ma) increase in downslope transport may have been related to the drowning of the Queensland Plateau. Site 822 (present depth, 955.2 m), at the base of the Great Barrier Reef slope, deepened from the upper bathyal to the middle bathyal zone during the late Pliocene (by ~2.3 Ma). Queensland Trough Site 823 (present depth, 1638.4 m) deepened from the middle bathyal to the lower bathyal (1000-2000 m) zone during the late Miocene (~6.5 Ma). Benthic foraminiferal faunal changes at these Leg 133 sites indicate that rapid deepening occurred during the middle Miocene (~13-14 Ma), late Miocene (6-7 Ma), and late Pliocene (2-3 Ma) along the northeastern Australian margin.

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes: Part 14. The infrared and Raman characteristics of phthalocyanine in “pinwheel-like” homoleptic bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato] rare earth(III) double-decker complexes

The infrared (IR) spectroscopic data and Raman spectroscopic properties for a series of 13 “pinwheel-like” homoleptic bis(phthalocyaninato) rare earth complexes M[Pc(α-OC5H11)4]2 [M = Y and Pr–Lu except Pm; H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected and comparatively studied. Both the IR and Raman spectra for M[Pc(α-OC5H11)4]2 are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues, namely M(Pc)2 and M[Pc(OC8H17)8]2, but resemble (for IR) or are a bit more complicated (for Raman) than those of heteroleptic counterparts M(Pc)[Pc(α-OC5H11)4], revealing the decreased molecular symmetry of these double-decker compounds, namely S8. Except for the obvious splitting of the isoindole breathing band at 1110–1123 cm−1, the IR spectra of M[Pc(α-OC5H11)4]2 are quite similar to those of corresponding M(Pc)[Pc(α-OC5H11)4] and therefore are similarly assigned. With laser excitation at 633 nm, Raman bands derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. The IR spectra reveal that the frequencies of pyrrole stretching and pyrrole stretching coupled with the symmetrical CH bending of –CH3 groups are sensitive to the rare earth ionic size, while the Raman technique shows that the bands due to the isoindole stretchings and the coupled pyrrole and aza stretchings are similarly affected. Nevertheless, the phthalocyanine monoanion radical Pc′− IR marker band of bis(phthalocyaninato) complexes involving the same rare earth ion is found to shift to lower energy in the order M(Pc)2 > M(Pc)[Pc(α-OC5H11)4] > M[Pc(α-OC5H11)4]2, revealing the weakened π–π interaction between the two phthalocyanine rings in the same order.