Selbstassemblierte Monolagen und magnetisch strukturierte Submonolagen mit dia- und paramagnetischen Molekülen sowie Einzelmolekülmagneten auf Phthalocyanin- und Subphthalocyanin-Basis

Mit dieser Arbeit wurde die Selbstassemblierung von dia- und paramagnetischen Molekülen sowie Einzelmolekülmagneten auf Goldsubstraten und magnetisch strukturierten Substraten untersucht. Dazu wurden drei verschiedene Klassen an Phthalocyaninderivaten verwendet: Diamagnetische Subphthalocyanine, paramagnetische Phthalocyaninatometalle und Diphthalocyaninatolanthanidkomplexe. Alle synthetisierten Verbindungen sind peripher thioethersubstituiert. Die Alkylketten (a: n-C8H17, b: n-C12H25) vermitteln die Löslichkeit in vielen organischen Solventien und sorgen für eine geordnete Assemblierung auf einer Oberfläche, wobei die Bindung auf Gold hauptsächlich über die Schwefelatome stattfindet. Die aus Lösung abgeschiedenen selbstassemblierten Monolagen wurden mit XPS, NEXAFS-Spektroskopie und ToF-SIMS untersucht. Bei der Selbstassemblierung auf magnetisch strukturierten Substraten stehen die Moleküle unter dem Einfluss magnetischer Streufelder und binden bevorzugt nur in bestimmten Bereichen. Die gebildeten Submonolagen wurden zusätzlich mit X-PEEM untersucht. Die erstmals dargestellten Manganphthalocyanine [MnClPc(SR)8] 1 wurden ausgehend von MnCl2 erhalten. Hier fand bei der Aufarbeitung an Luft eine Oxidation zu Mangan(III) statt; +III ist die stabilste Oxidationsstufe von Mangan in Phthalocyaninen. Der Nachweis des axialen Chloridoliganden erfolgte mit Massenspektrometrie und FIR- sowie Raman-Spektroskopie. SQUID-Messungen haben gezeigt, dass die Komplexe 1 vier ungepaarte Elektronen haben. Bei den Subphthalocyaninen [BClSubpc(SR)6] 2 wurde der axiale Chloridoligand mit dem stäbchenförmigen Phenolderivat 29-H substituiert und die erfolgreiche Ligandensubstitution durch NMR- und IR-Spektroskopie sowie Massenspektrometrie an den Produkten [BSubpc(SR)6(29)] 30 belegt. Der Radikalcharakter der synthetisierten Terbiumkomplexe [Tb{Pc(SR)8}2] 3 wurde spektroskopisch nachgewiesen; SQUID-Messungen ergaben, dass es sich um Einzelmolekülmagnete mit einer Energiebarriere U des Doppelpotentialtopfs von 880 K oder 610 cm-1 bei 3a handelt. Zunächst wurden die SAMs der Komplexverbindungen 1, 2, 30 und 3 auf nicht magnetisch strukturierten Goldsubstraten untersucht. Die Manganphthalocyanine 1 bilden geordnete SAMs mit größtenteils flach liegenden Molekülen, wie die XPS-, NEXAFS- und ToF-SIMS-Analyse zeigte. Die Mehrzahl der Thioether-Einheiten ist auf Gold koordiniert und die Alkylketten zeigen ungeordnet von der Oberfläche weg. Bei der Adsorption findet eine Reduktion zu Mangan(II) statt und der axiale Chloridoligand wird abgespalten. Das beruht auf dem sog. Oberflächen-trans-Effekt. Im vorliegenden Fall übt die Metalloberfläche einen stärkeren trans-Effekt als der axiale Ligand aus, was bisher experimentell noch nicht beobachtet wurde. Die thioethersubstituierten Subphthalocyanine 2 und 30 sowie die Diphthalocyaninatoterbium-Komplexe 3 sind ebenfalls für SAMs geeignet. Ihre Monolagen wurden mit XPS und NEXAFS-Spektroskopie untersucht, und trotz einer gewissen Unordnung in den Filmen liegen die Moleküle jeweils im Wesentlichen flach auf der Goldoberfläche. Vermutlich sind bei diesen Systemen auch die Alkylketten größtenteils parallel zur Oberfläche orientiert. Im Gegensatz zu den Manganphthalocyaninen 1 tritt bei 2b, 30a, 30b und 3b neben der koordinativen Bindung der Schwefelatome auf Gold auch eine für Thioether nicht erwartete kovalente Au–S-Bindung auf, die durch C–S-Bindungsbruch unter Abspaltung der Alkylketten ermöglicht wird. Der Anteil, zu dem dieser Prozess stattfindet, scheint nicht mit der Molekülstruktur zu korrelieren. Selbstassemblierte Submonolagen auf magnetisch strukturierten Substraten wurden mit dem diamagnetischen Subphthalocyanin 2b hergestellt. Der Nachweis der Submonolagen war schwierig und gelang schließlich durch eine Kombination von ToF-SIMS, NEXAFS Imaging und X-PEEM. Die Analyse der ToF-SIMS-Daten zeigte, dass tatsächlich eine Modulation der Verteilung der Moleküle auf einem unterwärts magnetisch strukturierten Substrat eintritt. Mit X-PEEM konnte die magnetische Struktur der ferromagnetischen Schicht des Substrats direkt der Verteilung der adsorbierten Moleküle zugeordnet werden. Die Subphthalocyanine 2b adsorbieren nicht an den Domänengrenzen, sondern vermehrt dazwischen. Auf Substraten mit abwechselnd 6.5 und 3.5 µm breiten magnetischen Domänen binden die Moleküle bevorzugt in den Bereichen geringster magnetischer Streufeldgradienten, also den größeren Domänen. Solche Substrate wurden für die ToF-SIMS- und X-PEEM-Messungen verwendet. Bei größeren magnetischen Strukturen mit ca. 400 µm breiten Domänen, wie sie aufgrund der geringeren Ortsauflösung dieser Methode für NEXAFS Imaging eingesetzt wurden, binden die Moleküle dann in allen Domänen. Die diamagnetischen Moleküle werden nach dieser Interpretation aus dem inhomogenen Magnetfeld über der Probenoberfläche heraus gedrängt und verhalten sich analog makroskopischer Diamagnete. Die eindeutige Detektion der Moleküle auf den magnetisch strukturierten Substraten konnte bisher nur für die diamagnetischen Subphthalocyanine 2b erfolgen. Um die Interpretation ihres Verhaltens bei der Selbstassemblierung in einem inhomogenen Magnetfeld weiter voranzutreiben, wurde das Subphthalocyanin 37b dargestellt, welches ein stabiles organisches TEMPO-Radikal in seinem axialen Liganden enthält. Das paramagnetische Subphthalocyanin 37b sollte auf den magnetisch strukturierten Substraten in Regionen starker magnetischer Streufelder binden und damit das entgegengesetzte Verhalten zu den diamagnetischen Subphthalocyaninen 2b zeigen. Aus Zeitgründen konnte dieser Nachweis im Rahmen dieser Arbeit noch nicht erbracht werden.

The synthesis and characterisation of two new iron thioantimonates: [Fe(en)(3)](2)Sb2S5 center dot 0.55H(2)O and [Fe(en)(3)](2)Sb4S8

Two new iron thioantimonates, [Fe(en)(3)](2)Sb2S5 (.) 0.55H(2)O (1) and [Fe(en)(3)](2)Sb4S8 (2). were synthesised under solvothermal conditions from the reactions of Sb2S3, FeCl2 and S in the presence of ethylenediamine at 413 and 438 K, respectively. The products were characterised by single-crystal X-ray diffraction, elemental analysis and SQUID magnetometry. Compound 1 is unusual in containing isolated Sb2S54- anions formed from two corner-sharing SbS33- trigonal pyramids. These units are arranged in rippled layers, 4 A apart, parallel to the bc-plane. Octahedrally coordinated [Fe(en)(3)](2+) cations lie in depressions within these anionic layers. In compound (2), repeated corner linking of SbS33- trigonal pyramids generates SbS2- chains, which may be considered as a polymerised form of the Sb2S54- anions in 1. The SbS2- chains are separated by [Fe(en)(3)](2+) cations. In both compounds, there is an extensive network of hydrogen bonds between the nitrogen atoms of the ethylenediamine ligands and the sulfur atoms of the anions and, in the case of 1, the uncoordinated water molecule. (c) 2005 Elsevier Ltd. All rights reserved.

Structure determination, magnetic and optical properties of a new chromium(II) thioantimonate, [Cr((NH2CH2CH2)(3)N)]Sb4S7

The chromium(II) antimony(III) sulphicle, [Cr((NH2CH2CH2)(3)N)]Sb4S7, was synthesised under solvothermal conditions from the reaction of Sb2S3. Cr and S dissolved in tris(2-aminoethyl)amine (tren) at 438 K. The products were characterised by single-crystal X-ray diffraction. elemental analysis, SQUID magnetometry and diffuse reflectance spectroscopy. The compound crystallises in the monoclinic space group P2(1)/n with a = 7.9756(7), b = 10.5191(9), c = 25.880(2) angstrom and beta = 90.864(5)degrees. Alternating SbS33- trigonal pyramids and Sb36 semi-cubes generate Sb4S72- chains which are directly bonded to Cr(tren pendant units. The effective magnetic moment of 4.94(6)mu(B) shows a negligible orbital contribution, in agreement with expectations for Cr(II):d(4) in a (5)A ground state. The measured band gap of 2.14(3) eV is consistent with a correlation between optical band gap and framework density that is established from analysis of a wide range of antimony sulphides. (C) 2007 Elsevier Ltd. All rights reserved.

[Cr(C6H18N4)(SbS3)], a chromium complex containing an unusual bidentate SbS33- ligand

A new chromium-antimony-sulfide, [Cr(C6H18N4)(SbS3)], has been synthesised under solvothermal conditions from CrCl3. 6H(2)O, Sb2S3 and S in the presence of triethylenetetramine at 433 K and characterised by single-crystal X-ray diffraction, thermogravimetry, elemental analysis and SQUID magnetometry. The structure of [Cr(C6H18N4)(SbS3)] consists of neutral mononuclear chromium-centred complexes, in which the Cr3+ is chelated by one tetradentate triethylenetetramine molecule and a bidentate SbS33- ligand, yielding distorted octahedral coordination. Intermolecular hydrogen bonds link individual molecules into layers within the ac plane. Within a layer, molecules occur in pairs with each member related by a centre of inversion. The Cr...Cr separation within a pair is approximately 6.5 Angstrom. Magnetic susceptibility data reveal Curie-Weiss behaviour with mu(eff) = 3.819(3)/mu(B) and a negligible Weiss constant, indicative of non-interacting Cr3+ ions. (C) 2003 Elsevier Science Ltd. All rights reserved.

Developing sensorized arm skin for an octopus inspired robot

Soft skin artefacts made of knitted nylon reinforced silicon rubber were fabricated mimicking octopus skin. A combination of ecoflex 0030 and 0010 were used as matrix of the composite to obtain the right stiffness for the skin artefacts. Material properties were characterised using static uniaxial tension and scissors cutting tests. Two types of tactile sensors were developed to detect normal contact; one used quantum tunnelling composite materials and the second was fabricated from silicone rubber and a conductive textile. Sensitivities of the sensors were tested by applying different modes of loading and the soft sensors were incorporated into the skin prototype. Passive suckers were developed and tested against squid suckers. An integrated skin prototype with embedded deformable sensors and attached suckers developed for the arm of an octopus inspired robot is also presented.

Structural, magnetic, and electronic properties of VxCr2−xS3(0

A new family of vanadium-substituted chromium sulfides (VxCr2-xS3, 0 < x < 2) has been prepared and characterized by powder X-ray and neutron diffraction, SQUID magnetometry, electrical resistivity, and Seebeck coefficient measurements. Vanadium substitution leads to a single-phase region with a rhombohedral Cr2S3 structure over the composition range 0.0 < x e 0.75, while at higher vanadium contents (1.6 e x < 2.0) a second single-phase region, in which materials adopt a cation-deficient Cr3S4 structure, is observed. Materials with the Cr2S3 structure all exhibit semiconducting behavior. However, both transport and magnetic properties indicate an increasing degree of electron delocalization with increasing vanadium content in this compositional region. Materials that adopt a Cr3S4-type structure exhibit metallic behavior. Magnetic susceptibility data reveal that all materials undergo a magnetic ordering transition at temperatures in the range 90–118 K. Low-temperature magnetization data suggest that this involves a transition to a ferrimagnetic state.

Thiocyanate complexes of uranium in multiple oxidation states: a combined structural, magnetic, spectroscopic, spectroelectrochemical, and theoretical study

A comprehensive study of the complexes A4[U(NCS)8] (A = Cs, Et4N, nBu4N) and A3[UO2(NCS)5] (A = Cs, Et4N) is described, with the crystal structures of [nBu4N]4[U(NCS)8]·2MeCN and Cs3[UO2(NCS)5]·O0.5 reported. The magnetic properties of square antiprismatic Cs4[U(NCS)8] and cubic [Et4N]4[U(NCS)8] have been probed by SQUID magnetometry. The geometry has an important impact on the low-temperature magnetic moments: at 2 K, μeff = 1.21 μB and 0.53 μB, respectively. Electronic absorption and photoluminescence spectra of the uranium(IV) compounds have been measured. The redox chemistry of [Et4N]4[U(NCS)8] has been explored using IR and UV–vis spectroelectrochemical methods. Reversible 1-electron oxidation of one of the coordinated thiocyanate ligands occurs at +0.22 V vs Fc/Fc+, followed by an irreversible oxidation to form dithiocyanogen (NCS)2 which upon back reduction regenerates thiocyanate anions coordinating to UO22+. NBO calculations agree with the experimental spectra, suggesting that the initial electron loss of [U(NCS)8]4– is delocalized over all NCS– ligands. Reduction of the uranyl(VI) complex [Et4N]3[UO2(NCS)5] to uranyl(V) is accompanied by immediate disproportionation and has only been studied by DFT methods. The bonding in [An(NCS)8]4– (An = Th, U) and [UO2(NCS)5]3– has been explored by a combination of DFT and QTAIM analysis, and the U–N bonds are predominantly ionic, with the uranyl(V) species more ionic that the uranyl(VI) ion. Additionally, the U(IV)–NCS ion is more ionic than what was found for U(IV)–Cl complexes.

The interplay of metal-atom ordering, Fermi leveltuning and thermoelectric properties in cobalt shandites Co3M2S2 (M = Sn, In)

A combination of structural, physical and computational techniques including powder X-ray and neutron diffraction, SQUID magnetometry, electrical and thermal transport measurements, DFT calculations and 119Sn Mössbauer and X-ray photoelec-tron spectroscopies has been applied to Co3Sn2-xInxS2 (0 ≤ x ≤ 2) in an effort to understand the relationship between metal-atom ordering and physical properties as the Fermi level is systematically varied. Whilst solid solution behavior is found throughout the composition region, powder neutron diffraction reveals that indium preferentially occupies an inter-layer site over an alternative kagome-like intra-layer site. DFT calculations indicate that this ordering, which leads to a lowering of energy, is related to the dif-fering bonding properties of tin and indium. Spectroscopic data suggest that throughout the composition range 0 ≤ x ≤ 2, all ele-ments adopt oxidation states that are significantly reduced from expectations based on formal charges. Chemical substitution ena-bles the electrical transport properties to be controlled through tuning of the Fermi level within a region of the density of states, which comprises narrow bands of predominantly Co d-character. This leads to a compositionally-induced double metal-to-semiconductor-to-metal transition. The marked increase in the Seebeck coefficient as the semiconducting region is approached leads to a substantial improvement in the thermoelectric figure of merit, ZT, which exhibits a maximum of ZT = 0.32 at 673 K. At 425 K, the figure of merit for phases in the region 0.8 ≤ x ≤ 0.85 is amongst the highest reported for sulphide phases, suggesting these materials may have applications in low-grade waste heat recovery.

Compositional control of the electrical transport properties in the new series of thiospinels Ga1-xGexV4S8-delta (0 <=x<=1)

A new series of non-stoichiometric sulfides Ga1−xGexV4S8−δ (0≤x≤1; δ≤0.23) has been synthesized at high temperatures by heating stoichiometric mixtures of the elements in sealed quartz tubes. The samples have been characterized by powder X-ray diffraction, SQUID magnetometry and electrical transport-property measurements. Structural analysis reveals that a solid solution is formed throughout this composition range, whilst thermogravimetric data reveal sulfur deficiency of up to 2.9% in the quaternary phases. Magnetic measurements suggest that the ferromagnetic behavior of the end-member phase GaV4S8 is retained at x≤0.7; samples in this composition range showing a marked increase in magnetization at low temperatures. By contrast Ga0.25Ge0.75V4S8−δ appears to undergo antiferromagnetic ordering at ca. 15 K. All materials with x≠1 are n-type semiconductors whose resistivity falls by almost six orders of magnitude with decreasing Ga content, whilst the end-member phase GeV4S8−δ is a p-type semiconductor. The results demonstrate that the physical properties are determined principally by the degree of electron filling of narrow-band states arising from intracluster V–V interactions.

The impact of charge transfer and structural disorder on the thermoelectric properties of cobalt intercalated TiS2

A family of phases, CoxTiS2 (0 ≤ x ≤ 0.75) has been prepared and characterised by powder X-ray and neutron diffraction, electrical and thermal transport property measurements, thermal analysis and SQUID magnetometry. With increasing cobalt content, the structure evolves from a disordered arrangement of cobalt ions in octahedral sites located in the van der Waals’ gap (x ≤ 0.2), through three different ordered vacancy phases, to a second disordered phase at x ≥ 0.67. Powder neutron diffraction reveals that both octahedral and tetrahedral inter-layer sites are occupied in Co0.67TiS2. Charge transfer from the cobalt guest to the TiS2 host affords a systematic tuning of the electrical and thermal transport properties. At low levels of cobalt intercalation (x < 0.1), the charge transfer increases the electrical conductivity sufficiently to offset the concomitant reduction in |S|. This, together with a reduction in the overall thermal conductivity leads to thermoelectric figures of merit that are 25 % higher than that of TiS2, ZT reaching 0.30 at 573 K for CoxTiS2 with 0.04 ≤ x ≤ 0.08. Whilst the electrical conductivity is further increased at higher cobalt contents, the reduction in |S| is more marked due to the higher charge carrier concentration. Furthermore both the charge carrier and lattice contributions to the thermal conductivity are increased in the electrically conductive ordered-vacancy phases, with the result that the thermoelectric performance is significantly degraded. These results illustrate the competition between the effects of charge transfer from guest to host and the disorder generated when cobalt cations are incorporated in the inter-layer space.

Estudo experimental e teórico das propriedades magnéticas e supercondutoras dos compostos borocarbetos da série Y(Ni 1-x Mn x) 2 B2 C com x = 0,0, 0,01, 0,025, 0,05, 0,10 e 0,15

Apresentamos neste trabalho os resultados de um estudo experimental e teórico dos compostos borocarbetos supercondutores da série Y(Ni1-xMnx)2B2C com x = 0; 0,01; 0,025; 0,05; 0,10; 0,15. A principal motivação para este trabalho foi investigar a estrutura eletrônica e a possível formação do momento magnético sobre os átomos de impureza de Mn nos compostos Y(Ni1- xMnx)2B2C. O aparecimento do momento magnético localizado no sítio da impureza possibilitou estudar a influência do Mn sobre o mecanismo de quebra de pares supercondutores e sobre as propriedades magnéticas do composto. Os borocarbetos são compostos de estrutura cristalina tetragonal de corpo centrado e altamente anisotrópicos (c/a~3). São intermetálicos de alta temperatura crítica supercondutora Tc, com forte acoplamento elétron-fonon. Em alguns casos podem apresentar ordem magnética, supercondutividade e também coexistência ou competição energética entre ambos. As medidas de transporte eletrônico, em função da temperatura, foram feitas utilizando-se um detector síncroton baseado na técnica de quatro pontos operando na faixa de 4,2K até 300K. Essas medidas possibilitaram o estudo das propriedades relacionadas ao transporte eletrônico na fase supercondutora. Na fase normal, extraiu-se a dependência em energia da função espectral de fonons α² F (ω) para alguns compostos da série estudada. As medidas magnéticas em função da temperatura e do campo magnético foram feitas utilizando-se um SQUID (Superconducting Quantun Interference Device – Quantun Design Model MPMS XL). Tais medidas permitiram a caracterização das propriedades magnéticas de nossas amostras. Em particular determinou-se o valor, em regime de saturação, do momento magnético associado ao sítio cristalino do Mn. Foram determinadas também as correntes críticas supercondutoras usando o Modelo de estado crítico de Bean e a variação da temperatura crítica supercondutora (Tc) com a mudança do campo externo aplicado. As medidas magnéticas permitiram a obtenção do diagrama que relaciona o campo crítico inferior (HC1) e a temperatura, variando-se a concentração do átomo dopante de manganês. Foi feito um esforço teórico no sentido de interpretar os resultados experimentais. Para isso foram usados três modelos: O modelo de estado crítico de Bean já citado acima e um modelo baseado na fórmula de Ziman usando uma aproximação para a função espectral de fonons para descrever a resistividade no regime de alta temperatura. Além disto, usou-se o modelo de duas sub-redes para a descrição do momento magnético das impurezas de Mn, em função da concentração, na série Y(Ni ) ( 2 ω α F 1-xMnx)2B2C.

Caracterização da captura incidental de tartarugas marinhas pela pesca de espinhel pelágico no Nordeste do Brasil

The marine turtles biological characteristics and the impact they have been suffering in consequence of human activities have caused in the last decades the decrease of populations to unsustainable levels. All four of the species described in this paper are registered as endangered in a list by IUCN: Caretta caretta, Lepidochelys olivacea, Chelonia mydas, Dermochelys coriacea. The main causes of such impact include several fishing activities, mostly the surface longline. This paper discusses the monitoring of two foreigner longline fleet along the North East Brazilian coast between October of 2004 and September of 2005. Both operated in the West South Atlantic, one using the Chinese technique and the other the American. The American method s target species is the swordfish (Xiphias gladius), and it is characterized by using squid as bait, J 9/0 offset 5º hook, light sticks and night soaking. It also operates in shallower waters than the Chinese method. The source of information about the efforts and the catches came from onboard observers and were used to calculate the catching rate of turtles over 1000 hooks (CPUE). The American equipment caught more turtles (CPUE = 0,059; N= 103), mainly D. coriacea, while the Chinese longline caught mainly the L. olivacea and presented a CPUE= 0,018 (N= 89). The hooks were most frequently found attached to the mouth of C. caretta, C. mydas, and L. olivacea. The D. coriacea were most frequently caught by hooks externally attached to different parts of their body. There was no significant difference between the hook type catching and most turtles were still alive when released. The results suggest a greater potential of turtle catching by the American method. Besides the statistic tests have showed less interaction between the Chinese equipment and marine turtles, the catches of this fishing technique could have been underestimated due to miscommunication between the onboard observer and the vessel s crew plus the retrieve of the longline during night time

Are deep-sea cephalopods really common preys for oceanic seabirds?

Uma análise de dados publicados sobre dietas de aves marinhas oceânicas mostra a predominância de cefalópodes musculares e de distribuição mais superficial nas camadas oceânicas, mas também são importantes as espécies gelatinosas e amoniacais restritas a camadas abaixo dos 300 m da superfície. A princípio, não deveria se esperar que cefalópodes de profundidade fossem considerados presas comuns de aves marinhas oceânicas como reportados por muitos autores. É proposto neste estudo que uma fonte indireta, importante e de fácil obtenção, surgiu com o início das atividades dos barcos atuneiros que operam com espinhel. O hábito de ingerir restos de vísceras de peixes capturados em barcos espinheleiros pode explicar as prováveis conclusões equivocadas de que cefalópodes de profundidade são presas naturais de aves marinhas oceânicas.

Chemical deposition of La0.7Ca0.3MnO3±δ films on ceramic substrates

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Magnetic response of superconducting mesoscopic-size YBCO powder

In this work it is reported the magnetic behavior of submicron and mesoscopic-size superconducting YBCO powders, prepared by a modified polymeric precursors method. The grain size and microstructure were analyzed using scanning electron microscopy ( SEM). Measurements of magnetization and AC-susceptibility as a function of temperature were performed with a quantum design SQUID magnetometer. Our results indicated significant differences on the magnetic propreties, in connection with the calcination temperature and the pressure used to pelletize the samples. This contribution is part of an effort to study vortex dynamics and magnetic properties of submicron and mesoscopic-size superconducting samples. (C) 2008 Elsevier B. V. All rights reserved.