Local polarity in CO2-expanded acetonitrile: a nucleophilic substitution reaction and solvatochromic probes

Many processes that use highly tunable gas-expanded liquids (GXLs) rely on the fact that CO2 addition can greatly affect the polarity of the solvent. We have examined several measures of bulk and local polarity in CO2-expanded acetonitrile to enable more effective exploitation of these polarity changes. The rate of the nucleophilic substitution reaction of tributylamine with methyl p-nitrobenzenesulfonate has been analyzed as a function of solvent composition by using in situ high-pressure UV/vis spectroscopy. We have also measured solvatochromic properties including the Kamlet-Taft pi* parameter and Kosower's Z-value. We correlate these local polarity-based kinetic and solvatochromic measures to develop a better understanding of these property changes as a function of bulk and local solvent composition. The data suggest that local composition enhancement in CO2-expanded acetonitrile has a significant impact on the reaction kinetics.     

Variable temperature neutron diffraction and X-ray charge density studies of tetraacetylethane

Single crystal neutron diffraction data have been collected on a sample of enolized 3,4-diacetyl-2,5-hexanedione (tetraacetylethane, TAE) at five temperatures between 20 and 298 K to characterize the temperature-dependent behavior of the short, strong, intramolecular hydrogen bond. Upon decreasing the temperature from 298 K to 20 K, the O2-H1 distance decreases from 1.171(11) to 1.081(2) A and the O1...H1 distance increases from 1.327(10) to 1.416(6) A. The convergence of the C-O bond lengths from inequivalent distances at low temperature to identical values (1.285(4) A) at 298 K is consistent with a resonance-assisted hydrogen bond. However, a rigid bond analysis indicates that the structure at 298 K is disordered. The disorder vanishes at lower temperatures. Short intermolecular C-H...O contacts may be responsible for the ordering at low temperature. The intramolecular O...O distance (2.432 +/- 0.006 A) does not change with temperature. X-ray data at 20 K were measured to analyze the charge density and to gain additional insight into the nature of the strong hydrogen bond. Quantum mechanical calculations demonstrate that periodic boundary conditions provide significant enhancement over gas phase models in that superior agreement with the experimental structure is achieved when applying periodicity. One-dimensional potential energy calculations followed by quantum treatment of the proton reproduce the location of the proton nearer to the O2 site reasonably well, although they overestimate the O-H distance at low temperatures. The choice of the single-point energy calculation strategy for the proton potential is justified by the fact that the proton is preferably located nearer to O2 rather than being equally distant to O1 and O2 or evenly distributed (disordered) between them.     

A bridging hexazene (RNNNNNNR) ligand from reductive coupling of azides

This communication reports the first examples of transition metal complexes containing an RNNNNNNR 2- ligand. Addition of 1-azidoadamantane to the diiron(I) synthon LRFeNNFeL R (L R = HC[C(R)N(2,6- iPr 2C 6H 3)] 2; R = methyl, tert-butyl) leads to the diiron complexes L RFe(mu-eta2:eta2-AdN6Ad)FeLR, which are surprisingly thermally stable. Magnetic, M?ssbauer, and crystallographic data are consistent with pairs of high-spin iron(II) ions antiferromagnetically coupled through a dianionic AdN6Ad 2- bridge.     

Materials Chemistry in Münster

Ende August haben Sigma‐Aldrich High‐Technology und die NRW Graduate School of Chemistry ihren zweiten gemeinsamen Doktoranden‐Workshop in Materials Chemistry veranstaltet. Mehr als 60 Doktoranden aus dem In‐ und Ausland haben drei Tage in den Münsteraner chemischen Instituten über Materialwissenschaften diskutiert.     

Mathematics, Experiments, and Theoretical Physics: The Early Days of the Sommerfeld School

Arnold Sommerfeld (1868-1951) founded one of the most influential schools of twentieth-century theoretical physics. His favored specialty was atomic theory, and a world-wide community of physicists was introduced to this field by his legendary textbook, Atomic Structure and Spectral Lines. The names of his students read like a Who's Who of the pioneers in modern physics Peter Debye, Peter Paul Ewald, Wolfgang Pauli, Werner Heisenberg, Hans A. Bethe - to name only the most prominent. In retrospect, the success of Sommerfeld's school of modern theoretical physics tends to overshadow its less glorious beginnings. A century ago, theoretical physics was not yet considered as a distinct discipline. In this article I emphasize more the haphazard beginnings than the later achievements of Sommerfeld's school, which mirrored the state of theoretical physics before it became an independent discipline.     

Synthesis of Amphiphilic Fullerene Derivatives and Their Incorporation in Langmuir and Langmuir‐Blodgett Films

Various amphiphilic fullerene derivatives were prepared by functionalization of [5,6]fullerene‐C₆₀‐I_h (C₆₀) with malonate or bis‐malonate derivatives obtained by esterification of the malonic acid mono‐esters 5 – 7 . Cyclopropafullerene 10 was obtained by protection of the carboxylic acid function of 6 as a tert‐butyl ester, followed by Bingel addition to C₆₀ and a deprotection step (Scheme 2). The preparation of 10 was also attempted directly from the malonic acid mono‐ester 6 under Bingel conditions. Surprisingly, the corresponding 3′‐iodo‐3′H‐cyclopropa[1,9][5,6]fullerene‐C₆₀‐I_h‐3′‐carboxylate 11 was formed instead of 10 (Scheme 3). The general character of this new reaction was confirmed by the preparation of 15 and 16 from the malonic acid mono‐esters 13 and 14 , respectively (Scheme 4). All the other amphiphilic fullerene derivatives were prepared by taking advantage of the versatile regioselective reaction developed by Diederich and co‐workers which led to macrocyclic bis‐adducts of C₆₀ by a cyclization reaction at the C‐sphere with bis‐malonate derivatives in a double Bingel cyclopropanation. The bis‐adducts 37 – 39 with a carboxylic acid polar head group and four pendant long alkyl chains of different length were prepared from diol 22 and acids 5 – 7 , respectively (Scheme 9). In addition, the amphiphilic fullerene derivatives 45, 46, 49, 54 , and 55 bearing different polar head groups and compound 19 with no polar head group were synthesized (Schemes 11–13, 15, and 5, resp.). The ability of all these compounds to form Langmuir monolayers at the air‐water interface was investigated in a systematic study. The films at the water surface were characterized by their surface pressure vs. molecular area isotherms, compression and expansion cycles, and Brewster‐angle microscopy. The spreading behavior of compound 10 was not good, the two long alkyl chains in 10 being insufficient to prevent aggregation resulting from the strong fullerene‐fullerene interactions. While no films could be obtained from compound 19 with no polar head group, all the corresponding amphiphilic fullerene bis‐adducts showed good spreading characteristics and reversible behavior upon successive compression/expansion cycles. The encapsulation of the fullerene in a cyclic addend surrounded by four long alkyl chains is, therefore, an efficient strategy to prevent the irreversible aggregation resulting from strong fullerene‐fullerene interactions usually observed for amphiphilic C₆₀ derivatives at the air‐water interface. The balance of hydrophobicity to hydrophilicity was modulated by changing the length of the surrounding alkyl chains or the nature of the polar head group. The best results in terms of film formation and stability were obtained with the compounds having the largest polar head group, i.e. 45 and 46 , and dodecyl chains. Finally, the Langmuir films obtained from the amphiphilic fullerene bis‐adducts were transferred onto solid substrates, yielding high‐quality Langmuir‐Blodgett films.     

Amphiphilic and mesomorphic fullerene-based dendrimers

Growing attention is currently devoted to large dendritic structures for applications in nanotechnology and materials science. In this respect, the incorporation of such compounds into thin ordered films appears to be an important issue. One of the most widely pursued approaches to structurally ordered dendrimer assemblies has been the preparation of Langmuir films at the air-water interface. We report on the case of a diblock globular fullerene-based dendrimer and show that peripheral substitution of the dendrimer with hydrophobic chains on one hemisphere and hydrophilic groups on the other provides the required hydrophobic/hydrophilic balance allowing the formation of stable Langmuir films. A second approach has been to consider the case of fullerene containing dendrimers terminated by mesogenic groups such as cyanobiphenyl subunits. Whatever the generation is, up to the fourth one, all these compounds exhibit a well-defined liquid crystalline smectic A phase. The molecular organisation within the smectic layers is found to be monolayered or bilayered depending on the generation. For the smallest dendrimers, the organisation is mainly governed by the size of the fullerene moiety, whereas for the higher ones, it is governed by the interactions between the terminal mesogenic groups. These two approaches appear particularly interesting for functional groups such as fullerenes, which are not well adapted to be organised in nanoscale architectures. The present study shows that fullerenes can indeed be introduced into different types of ordered structure when they have been chemically adequately modified.     

Preparation of an Organometallic Molecular Square by Self‐Assembly of Phosphorus‐Containing Building Blocks

Molecular squares are among the most common supramolecular architectures, but phospha‐organometallic complexes have not been used as building blocks for this type of structure. Herein we describe the formation of the molecular square [Au{Co(P₂C₂tBu₂)₂}]₄ ( 1 ) by the self‐assembly of anionic 1,3‐diphosphacyclobutadiene cobalt complexes and gold(I) cations. The X‐ray crystallographic determination of the molecular structure of 1 is complemented by solid‐state ³¹P and ¹³C NMR investigations. High‐level DFT calculations confirm the assignment of the ³¹P and ¹³C NMR resonances.