Glacial North Atlantic: Sea surface conditions reconstructed by GLAMAP 2000

The response of the tropical ocean to global climate change and the extent of sea ice in the glacial nordic seas belong to the great controversies in paleoclimatology. Our new reconstruction of peak glacial sea surface temperatures (SSTs) in the Atlantic is based on census counts of planktic foraminifera, using the Maximum Similarity Technique Version 28 (SIMMAX-28) modern analog technique with 947 modern analog samples and 119 well-dated sediment cores. Our study compares two slightly different scenarios of the Last Glacial Maximum (LGM), the Environmental Processes of the Ice Age: Land, Oceans, Glaciers (EPILOG), and Glacial Atlantic Ocean Mapping (GLAMAP 2000) time slices. The comparison shows that the maximum LGM cooling in the Southern Hemisphere slightly preceeded that in the north. In both time slices sea ice was restricted to the north western margin of the nordic seas during glacial northern summer, while the central and eastern parts were ice-free. During northern glacial winter, sea ice advanced to the south of Iceland and Faeroe. In the central northern North Atlantic an anticyclonic gyre formed between 45° and 60°N, with a cool water mass centered west of Ireland, where glacial cooling reached a maximum of >12°C. In the subtropical ocean gyres the new reconstruction supports the glacial-to-interglacial stability of SST as shown by CLIMAP Project Members (CLIMAP) [1981]. The zonal belt of minimum SST seasonality between 2° and 6°N suggests that the LGM caloric equator occupied the same latitude as today. In contrast to the CLIMAP reconstruction, the glacial cooling of the tropical east Atlantic upwelling belt reached up to 6°-8°C during Northern Hemisphere summer. Differences between these SIMMAX-based and published U37[k]- and Mg/Ca-based equatorial SST records are ascribed to strong SST seasonalities and SST signals that were produced by different planktic species groups during different seasons.

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.

Peripherally η1-Platinated Organometallic Porphyrins as Building Blocks for Multiporphyrin Arrays

The modification of peripherally metalated meso-η1-platiniometalloporphyrins, such as trans-[PtBr(NiDAPP)(PPh3)2] (H2DAPP = 5-phenyl-10,20-bis(3‘,5‘-di-tert-butylphenyl)porphyrin), leads to the analogous platinum(II) nitrato and triflato electrophiles in almost quantitative yields. Self-assembly reactions of these meso-platinioporphyrin tectons with pyridine, 4,4‘-bipyridine, or various meso-4-pyridylporphyrins in chloroform generate new multicomponent organometallic porphyrin arrays containing up to five porphyrin units. These new types of supramolecular arrays are formed exclusively in high yields and are stable in solution or in the solid state for extended periods. They were characterized by multinuclear NMR and UV−visible spectroscopy as well as high-resolution electrospray ionization mass spectrometry.