Supramolecular hydrogen-bond structures and magnetic interactions in basal-apical, dinuclear, azide-bridged copper(II) complexes

The synthesis, characterisation, X-ray single crystal structures and magnetic properties of three new basal-apical mu(2)-1,1-azide-bridged complexes [(CuLN3)-N-1](2) (1), [(CuLN3)-N-2](2) (2) and [(CuLN3)-N-3](2) (3) with very similar tridentate Schiff-base blocking ligands {HL1 = N-[2-(ethylamino) ethyl] salicylaldimine; HL2 = 7-(ethylamino)-4-methyl-5-azahept-3-en-2-one; HL3 = 7-amino-4-methyl-5-azaoct-3-en-2-one} have been reported [complex 1: monoclinic, P2(1)/c, a = 8.390(2), b = 7.512(2), c = 19.822(6) Angstrom, beta = 91.45(5)degrees; complex 2: monoclinic, P2(1)/c, a = 8.070(9), b = 9.787(12), c = 15.743(17) A, beta = 98.467(10)degrees; complex 3: monoclinic, P2(1)/n, a = 5.884(7), b = 16.147(18), c = 11.901(12) Angstrom, beta = 90.050(10)degrees]. The structures consist of neutral dinuclear entities resulting from the pairing of two mononuclear units through end-on azide bridges connecting an equatorial position of one copper centre to an axial position of the other, The copper ions adopt a (4+1) square-based geometry in all the complexes. In complex 2, there is no inter-dimer hydrogen-bonding. However, complexes 1 and 3 form two different supramolecular structures in which the dinuclear entities are linked by H-bonds giving one-dimensional systems. Variable temperature (300-2 K) magnetic-susceptibility measurements and magnetisation measurements at 2 K reveal that all three complexes have antiferromagnetic coupling. Magneto-structural correlations have been made taking into consideration both the azido bridging ligands and the existence of intermolecular hydrogen bonds. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

From apotheosis to damnation: Mussolini and the Fascist regime, 1936-45

This is an essay for a catalogue of the exhibition 'Against Mussolini: art and the fall of a dictator' held at the Estorick Collection, London, September - December 2010. The essay examines shifting attitudes towards Mussolini in the years immediately preceding his fall, and suggests that the development of 'anti-fascism' was less pronounced than often suggested.

A 45 kyr palaeoclimate record from the lowland interior of tropical South America

We present a well-dated, high-resolution, ~ 45 kyr lake sediment record reflecting regional temperature and precipitation change in the continental interior of the Southern Hemisphere (SH) tropics of South America. The study site is Laguna La Gaiba (LLG), a large lake (95 km2) hydrologically-linked to the Pantanal, an immense, seasonally-flooded basin and the world's largest tropical wetland (135,000 km2). Lake-level changes at LLG are therefore reflective of regional precipitation. We infer past fluctuations in precipitation at this site through changes in: i) pollen-inferred extent of flood-tolerant forest; ii) relative abundance of terra firme humid tropical forest versus seasonally-dry tropical forest pollen types; and iii) proportions of deep- versus shallow-water diatoms. A probabilistic model, based on plant family and genus climatic optima, was used to generate quantitative estimates of past temperature from the fossil pollen data. Our temperature reconstruction demonstrates rising temperature (by 4 °C) at 19.5 kyr BP, synchronous with the onset of deglacial warming in the central Andes, strengthening the evidence that climatic warming in the SH tropics preceded deglacial warming in the Northern Hemisphere (NH) by at least 5 kyr. We provide unequivocal evidence that the climate at LLG was markedly drier during the last glacial period (45.0–12.2 kyr BP) than during the Holocene, contrasting with SH tropical Andean and Atlantic records that demonstrate a strengthening of the South American summer monsoon during the global Last Glacial Maximum (~ 21 kyr BP), in tune with the ~ 20 kyr precession orbital cycle. Holocene climate conditions occurred as early as 12.8–12.2 kyr BP, when increased precipitation in the Pantanal catchment caused heightened flooding and rising lake levels in LLG. In contrast to this strong geographic variation in LGM precipitation across the continent, expansion of tropical dry forest between 10 and 3 kyr BP at LLG strengthens the body of evidence for widespread early–mid Holocene drought across tropical South America.

A thermoreversible supramolecular polyurethane with excellent healing ability at 45 °C

We report the synthesis and characterization of a healable, elastomeric shape recovery supramolecular polyurethane whose properties result from self-complementary π−π stacking and hydrogen bonding interactions plus phase separation. ESEM analysis and photographic images have revealed that this material can heal at 45 °C in 15 min to recover the mechanical properties of the pristine material with healing efficiencies >99%. This supramolecular polyurethane is also able to recover an applied strain of 25% within 5 min of release of the load.