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11.
Schuster DI Cheng P Jarowski PD Guldi DM Luo C Echegoyen L Pyo S Holzwarth AR Braslavsky SE Williams RM Klihm G 《Journal of the American Chemical Society》2004,126(23):7257-7270
As part of a continuing investigation of the topological control of intramolecular electron transfer (ET) in donor-acceptor systems, a symmetrical parachute-shaped octaethylporphyrin-fullerene dyad has been synthesized. A symmetrical strap, attached to ortho positions of phenyl groups at opposing meso positions of the porphyrin, was linked to [60]-fullerene in the final step of the synthesis. The dyad structures were confirmed by (1)H, (13)C, and (3)He NMR, and MALDI-TOF mass spectra. The free-base and Zn-containing dyads were subjected to extensive spectroscopic, electrochemical and photophysical studies. UV-vis spectra of the dyads are superimposable on the sum of the spectra of appropriate model systems, indicating that there is no significant ground-state electronic interaction between the component chromophores. Molecular modeling studies reveal that the lowest energy conformation of the dyad is not the C(2)(v)() symmetrical structure, but rather one in which the porphyrin moves over to the side of the fullerene sphere, bringing the two pi-systems into close proximity, which enhances van der Waals attractive forces. To account for the NMR data, it is proposed that the dyad is conformationally mobile at room temperature, with the porphyrin swinging back and forth from one side of the fullerene to the other. The extensive fluorescence quenching in both the free base and Zn dyads is associated with an extremely rapid photoinduced electron-transfer process, k(ET) approximately 10(11) s(-)(1), generating porphyrin radical cations and C(60) radical anions, detected by transient absorption spectroscopy. Back electron transfer (BET) is slower than charge separation by up to 2 orders of magnitude in these systems. The BET rate is slower in nonpolar than in polar solvents, indicating that BET occurs in the Marcus inverted region, where the rate decreases as the thermodynamic driving force for BET increases. Transient absorption and singlet molecular oxygen sensitization data show that fullerene triplets are formed only with the free base dyad in toluene, where triplet formation from the charge-separated state is competitive with decay to the ground state. The photophysical properties of the P-C(60) dyads with parachute topology are very similar to those of structurally related rigid pi-stacked P-C(60) dyads, with the exception that there is no detectable charge-transfer absorption in the parachute systems, attributed to their conformational flexibility. It is concluded that charge separation in these hybrid systems occurs through space in unsymmetrical conformations, where the center-to-center distance between the component pi-systems is minimized. Analysis of the BET data using Marcus theory gives reorganization energies for these systems between 0.6 and 0.8 eV and electronic coupling matrix elements between 4.8 and 5.6 cm(-)(1). 相似文献
12.
Krahl T Stösser R Kemnitz E Scholz G Feist M Silly G Buzaré JY 《Inorganic chemistry》2003,42(20):6474-6483
The structure of the very strong solid Lewis acid aluminum chlorofluoride (ACF, AlCl(x)F(3-x), x = 0.05-0.3) was studied by IR, ESR, Cl K XANES, (19)F MAS NMR, and (27)Al SATRAS NMR spectroscopic methods and compared with amorphous aluminum fluoride conventionally prepared by dehydration of alpha-AlF(3) x 3H(2)O. The thermal behavior of both compounds was investigated by DTA and XRD. In comparison to ACF, amorphous AlF(3) prepared in a conventional way is not catalytically active for the isomerization reaction of 1,2-dibromohexafluoropropane, which requires a very strong Lewis acid. Both compounds are mainly built up of corner-sharing AlF(6) octahedra forming a random network. The degree of disorder in ACF is higher than in amorphous AlF(3). Terminal fluorine atoms were detected in ACF by (19)F NMR. The chlorine in ACF does not exist as a separate, crystalline AlCl(3) phase. Additionally, chlorine-containing radicals, remaining from the synthesis, are trapped in cavities of ACF. These radicals are stable at room temperature but do not take part in the catalytic reaction. 相似文献
13.
Maëva-Charlotte Kervarec Prof. Dr. Erhard Kemnitz Priv.-Doz. Dr. Gudrun Scholz Dr. Svemir Rudić Prof. Dr. Thomas Braun Prof. Dr. Christian Jäger Dr. Adam A. L. Michalchuk Priv.-Doz. Dr. Franziska Emmerling 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(32):7314-7322
The very strong Lewis acid aluminium chlorofluoride (ACF) was loaded with anhydrous HF. The interaction between the surface of the catalyst and HF was investigated using a variety of characterization methods, which revealed the formation of polyfluorides. Moreover, the reactivity of the HF-loaded ACF towards the hydrofluorination of alkynes was studied. 相似文献
14.
Gerd Becker Winfried Becker Gudrun Uhl Werner Uhl Hans-Jürgen Wessely 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-3):7-10
Abstract Alkyl- or arylbis(trimethylsilyl)phosphines as well as tris(trimethylsilyl)phosphine and the corresponding arsines react with acyl chlorides to give [1-(trimethylsiloxy)alkylidene]phosphines 1 and -arsines 2; most of their 2,2-dimethylpropylidene derivatives are thermally stable at room temperature. With the same class of phosphines as starting compounds and carbon disulfide [bis(trimethylsilylsulfano)methylidene]phosphines 3 are formed, whereas [(dialkylamino)methylidene]-4 and [diarylmethylidene]phosphines 5 or the corresponding arsines 6 and 7 can be obtained from acyl amides or ketones.1 相似文献
15.
Andreia Alves Agnieszka Kucharska Claudio Erratico Fuchao Xu Elly Den Hond Gudrun Koppen Guido Vanermen Adrian Covaci Stefan Voorspoels 《Analytical and bioanalytical chemistry》2014,406(17):4063-4088
Human biomonitoring (HBM) is a scientific technique that allows us to assess whether and to what extent environmental pollutants enter humans. We review here the current HBM efforts for organophosphate esters, emerging flame retardants, perfluoroalkyl substances, and phthalate esters. Use of some of these chemicals has already been banned or restricted; they are regularly detected in the environment, wildlife, and human matrices. Traditionally, blood and urine collection have been widely used as sampling methods. New non-invasive approaches (e.g., saliva, hair, nails) are emerging as valid alternatives since they offer advantages with respect to sampling, handling, and ethical aspects, while ensuring similar reliability and sensitivity. Nevertheless, the identification of biomarkers of exposure is often difficult because chemicals may be metabolized in the human body. For many of the above-mentioned compounds, the mechanisms of the favorable metabolization pathways have not been unraveled, but research on important metabolites that could be used as biomarkers of exposure is growing. This review summarizes the state of the art regarding human exposure to, (non-invasive) HBM of, and metabolism of major organophosphate esters, emerging flame retardants, perfluoroalkyl substances, and phthalate esters currently detected in the environment. Figure
Human biomonitoring of emerging contaminants-non-invasive versus invasive matrices 相似文献
16.
Composition of oxygen precipitates in Czochralski silicon wafers investigated by STEM with EDX/EELS and FTIR spectroscopy 下载免费PDF全文
Dawid Kot Gudrun Kissinger Markus Andreas Schubert Max Klingsporn Andreas Huber Andreas Sattler 《固体物理学:研究快报》2015,9(7):405-409
In this work, we investigated the stoichiometry of oxygen precipitates in Czochralski silicon wafers. The thickness dependence of the Cliff–Lorimer sensitivity factor for the silicon/oxygen system was determined and applied for the investigation of the stoichiometry of oxygen precipitates by EDX. The results show that both plate‐like oxygen precipitates and a transitional form between plate‐like and octahedral precipi‐ tates consist of SiO2. This was confirmed by EELS low loss spectra where the typical spectrum for amorphous SiO2 was observed. Moreover, the absorption band of plate‐like precipitates at 1227 cm–1 was found in the low temperature FTIR spectrum. It was demonstrated that this band can only be simulated by the dielectric constants of amorphous SiO2. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim) 相似文献
17.
The interaction between oppositely charged polyelectrolytes, in this study poly(diallyldimethylammonium chloride) (PDADMAC)
and copolymers of acrylamide and sodium-acrylate differing in their chain length and charge density parameter (ξ) was investigated
in relation to the molar charge ratio of anionic to cationic charges (n
−/n
+). The molecular weights of the polyelectrolytes used were 2.9·105 g/mol for PDADMAC and for the polyacrylamide copolymers 14 ·106 g/mol as well as 5·105 g/mol obtained by ultrasonic degradation of the high molecular weight copolymers. The charge density parameters of the polyanions
used (ξ
PR
) varied between 0.14 and 0.64. Complexation between PDADMAC and high molecular weight polyanions leads mainly to macroscopic
phase separation whereas the degraded polyanions and PDADMAC formed soluble complexes as well as stable dispersions, if charge
excess was available. Precipitates and dispersions were characterized by several methods such as element analysis, thermogravimetry,
pyrolysis-GC/MS, PEL titration, ζ-potential measurements, determination of turbidity, particle size measurements and determination
of carbon content (TOC).
All precipitated complexes include about 20% water and are of 1:1 stoichiometry concerning ionic binding. Investigations
of dispersions confirm 1:1 stoichiometry of complex particles stabilized by excess polyelectrolyte and soluble complexes.
It was also found that the particle size can be varied via the charge density parameter of the polyanions used in the range
of negative charge excess.
Received: 21 June 2001 Accepted: 9 October 2001 相似文献
18.
Rainer Niewa Andreas Czulucki Gudrun Auffermann Martin Meven Frank Steglich 《Journal of solid state chemistry》2010,183(6):1309-1313
Large single crystals of ZrAsxSey (x>y, x+y≤2, PbFCl type of structure, space group P4/nmm) were grown by Chemical Transport. Structural details were studied by single crystal neutron diffraction techniques at various temperatures. One single crystal specimen with chemical composition ZrAs1.595(3)Se0.393(1) was studied at ambient temperature (R1=5.10 %, wR2=13.18 %), and a second crystal with composition ZrAs1.420(3)Se0.560(1) was investigated at 25 K (R1=2.70%, wR2=5.70 %) and 2.3 K (R1=2.30 %, wR2=4.70 %), respectively. The chemical compositions of the crystals under investigation were determined by wavelength dispersive X-ray spectroscopy. The quantification of trace elements was carried out by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry. According to the crystal structure refinements the crystallographic 2a site is occupied by As, together with a significant amount of vacancies. One of the 2c sites is fully occupied by As and Se (random distribution). With respect to the fractional coordinates of the atoms, the crystal structure determinations based on the data obtained at 25.0 K and 2.3 K did not show significant deviations from ambient temperature results. The temperature dependence of the displacement parameters indicates a static displacement of As on the 2a sites (located on the (0 0 1) planes) for all temperatures. No indications for any occupation of interstitial sites or the presence of vacancies on the Zr (2a) site were found. 相似文献
19.
Dr. Thomas Lunkenbein Dr. Frank Girgsdies Anna Wernbacher Dr. Johannes Noack Dr. Gudrun Auffermann Akira Yasuhara Achim Klein‐Hoffmann Prof. Wataru Ueda Dr. Maik Eichelbaum Dr. Annette Trunschke Prof. Robert Schlögl Dr. Marc G. Willinger 《Angewandte Chemie (International ed. in English)》2015,54(23):6828-6831
Complex Mo,V‐based mixed oxides that crystallize in the orthorhombic M1‐type structure are promising candidates for the selective oxidation of small alkanes. The oxygen sublattice of such a complex oxide has been studied by annular bright field scanning transmission electron microscopy. The recorded micrographs directly display the local distortion in the metal oxygen octahedra. From the degree of distortion we are able to draw conclusions on the distribution of oxidation states in the cation columns at different sites. The results are supported by X‐ray diffraction and electron paramagnetic resonance measurements that provide integral details about the crystal structure and spin coupling, respectively. 相似文献
20.
Selective Template Removal by Thermal Depolymerization to Obtain Mesostructured Molybdenum Oxycarbide
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Martin Schieder Thomas Lunkenbein Carina Bojer Martin Dulle Julia vom Stein Gudrun Auffermann Tina Löbling Judith Schöbel Holger Schmalz Josef Breu 《无机化学与普通化学杂志》2015,641(10):1829-1834
The carbon content of mesostructured organic‐inorganic hybrid material of a cylindrical block copolymer template of poly(2‐vinylpyridine)‐block‐poly(allyl methacrylate) (P2VP‐b‐PAMA) and ammonium paramolybdate (APM) could be reduced by thermal depolymerization. By calcination in vacuo at 320 °C the PAMA core can be completely removed while the remaining P2VP brush preserves the mesostructure. The P2VP‐APM composite can then be carburized in‐situ to MoOxCy in a second pyrolysis step without any additional carbon source but P2VP. The molybdenum oxycarbide nanotubes obtained, form hierarchically porous non‐woven structures, which were tested as catalyst in the decomposition of NH3. They proved to be catalytically active at temperatures above 450 °C. The activation energy was estimated from an Arrhenius Plot to be 127 kJ · mol–1. 相似文献