Taking multicalixarenes into the nanoworld: first third-generation calixarene dendrimer

We report the first synthesis of a dendritic multicalixarene, featuring twenty-one calixarene units, which when adsorbed onto mica, forms regular assemblies which can then further aggregate to form larger clusters.     

Magnetic properties of Ni nanoparticles on microporous silica spheres

Ni nanoparticles (~32 nm particle diameter) have been synthesized on the walls of microporous (~1 nm pore diameter) silica spheres (~2.6 μm sphere diameter) and characterised magnetically to potentially produce a new class of core (silica micro-spheres)-shell (nanometallic)-type nanocomposite material. These magnetic nanocomposite materials display a characteristic increase in coercivity with reducing temperature. The average particle size has been used to calculate the anisotropy constant for the system, K. The discussion postulates the potential mechanisms contributing to the difference between the calculated K value and the magnetocrystalline anisotropy constant of bulk Ni. Various factors such as surface anisotropy and interparticle interactions are discussed as possible contributing factors to the anisotropy values calculated in the paper.     

A high-speed optical multi-drop bus for computer interconnections

Buses have historically provided a flexible communications structure in computer systems. However, signal integrity constraints of high-speed electronics have made multi-drop electrical buses infeasible. Instead, we propose an optical data bus for computer interconnections. It has two sets of optical waveguides, one as a fan-out and the other as a fan-in, that are used to interconnect different modules attached to the bus. A master module transmits optical signals which are received by all the slave modules attached to the bus. Each slave module in turn sends data back on the bus to the master module. Arrays of lasers, photodetectors, waveguides, microlenses, beamsplitters, and Tx/Rx integrated circuits are used to realize the optical data bus. With 1 mW of laser power, we are able to interconnect eight different modules at 10 Gb/s per channel. An aggregate bandwidth of over 25 GB/s is achievable with 10-bit wide signaling paths.     

Formation of FePt nanoparticles having high coercivity

Ultrasonication of toluene solutions of the heteropolynuclear cluster complex, Pt3Fe3(CO)15, in the presence of oleic acid and oleylamine affords surface-capped fcc FePt nanoparticles having an average diameter of ca. 2 nm. Self-assembled arrays of these nanoparticles on oxidized Si wafers undergo a fcc-to-fct phase transition at 775 degrees C to form ferromagnetic FePt nanocrystals ca. 5.8 nm in diameter well dispersed on the Si wafer surface. Room-temperature coercivity measurements of these annealed FePt nanoparticles confirm a high coercivity of ca. 22.3 kOe. Such high coercivity for fct FePt nanoparticles might result from use of a heterpolynuclear complex as a single-source precursor of Fe and Pt neutral atoms or from use of ultrasonication to form fcc FePt nanoparticles under conditions of exceptionally rapid heating. Experiments to determine the critical experimental conditions required to achieve such high room-temperature coercivities in ferromagnetic nanoparticles are underway.     

Heterometallic dithiolene complexes formed by stepwise displacement of cyclopentadienyl ligands from nickelocene with CpMo(S2C2Ph2)2

The dithiolene ligand transfer reaction between Ni(S2C2Ph2)2 (1) and CpMo(CO)3Cl (2; Cp = eta-C5H5) affords the neutral paramagnetic molybdenum bis(dithiolene) complex CpM(S2C2Ph2)2 (3), which has been structurally characterized. As found in other d1 complexes of this type, one dithiolene ligand is planar while the other is significantly folded toward the Cp ligand. An unexpected second product of the reaction is the unusual trinuclear species Ni[Mo(S2C2Ph2)2Cp]2 (4), which in the solid state contains three different dithiolene bonding modes (terminal, bridging, and semi-bridging) in the same molecule. Complex 4 can also be synthesized by displacement of the diene ligands in Ni(cod)2 with 2 equiv of 3. In contrast, the reaction of nickelocene with 3 proceeds by displacement of the Cp ligands in a stepwise manner to give initially the dinuclear species NiMo(mu-S2C2Ph2)2Cp2 5, which then reacts further with 3 to produce 4.     

Synthesis and structure of CpMo(CO)(dppe)H and its oxidation by Ph3C+

The reaction of CpMo(CO)(dppe)Cl (dppe = Ph2PCH2CH2PPh2) with Na+[AlH2(OCH2CH2OCH3)2]- gives the molybdenum hydride complex CpMo(CO)(dppe)H, the structure of which was determined by X-ray crystallography. Electrochemical oxidation of CpMo(CO)(dppe)H in CH3CN is quasi-reversible, with the peak potential at -0.15 V (vs Fc/Fc+). The reaction of CpMo(CO)(dppe)H with 1 equiv of Ph3C+BF4- in CD3CN gives [CpMo(CO)(dppe)(NCCD3)]+ as the organometallic product, along with dihydrogen and Gomberg's dimer (which is formed by dimerization of Ph3C.). The proposed mechanism involves one-electron oxidation of CpMo(CO)(dppe)H by Ph3C+ to give the radical-cation complex [CpMo(CO)(dppe)H].+. Proton transfer from [CpMo(CO)(dppe)H].+ to CpMo(CO)(dppe)H, loss of dihydrogen from [CpMo(CO)(dppe)(H)2]+, and oxidation of Cp(CO)(dppe)Mo. by Ph3C+ lead to the observed products. In the presence of an amine base, the stoichiometry changes, with 2 equiv of Ph3C+ being required for each 1 equiv of CpMo(CO)(dppe)H because of deprotonation of [CpMo(CO)(dppe)H].+ by the amine. Protonation of CpMo(CO)(dppe)H by HOTf provides the dihydride complex [CpMo(CO)(dppe)(H)2]+OTf-, which loses dihydrogen to generate CpMo(CO)(dppe)(OTf).     

Unprecedented [V2O]6+ core of a centrosymmetric thiosemicarbazonato dimer: spontaneous deoxygenation of oxovanadium(IV)

The complex cation [{V(daptsc)(MeOH)}2(mu-O)]2+ [daptsc(2-) = 2,6-diacetylpyridine bis(thiosemicarbazonate)] is the first crystallographically elucidated dimer to possess a [V2O]6+ core, the [V(IV)-O-V(IV)]6+ structural unit, formed by cleavage of the multiple bond in the oxo-cation VO2+, is linear with the oxo group residing on a crystallographic center of inversion, and the temperature dependence of the magnetic data of the dimer is consistent with weak antiferromagnetic coupling of the d1-d1 centers.     

Triplet correlation in sheared suspensions of Brownian particles

Triplet microstructure of sheared concentrated suspensions of Brownian monodisperse spherical particles is studied by sampling realizations of a three-dimensional unit cell subject to periodic boundary conditions obtained in accelerated Stokesian dynamics simulations. Triplets are regarded as a bridge between particle pairs and many-particle clusters thought responsible for shear thickening. Triplet-correlation data for weakly sheared near-equilibrium systems display an excluded volume effect of accumulated correlation for equilateral contacting triplets. As the Peclet number increases, there is a change in the preferred contacting isosceles triplet configuration, away from the "closed" triplet where the particles lie at the vertices of an equilateral triangle and toward the fully extended rod-like linear arrangement termed the "open" triplet. This transition is most pronounced for triplets lying in the plane of shear, where the open triplets' angular orientation with respect to the flow is very similar to that of a contacting pair. The correlation of suspension rheology to observed structure signals onset of larger clusters. An investigation of the predictive ability of Kirkwood's superposition approximation (KSA) provides valuable insights into the relationship between the pair and triplet probability distributions and helps achieve a better and more detailed understanding of the interplay of the pair and triplet dynamics. The KSA is seen more successfully to predict the shape of isosceles contacting triplet nonequilibrium distributions in the plane of shear than for similar configurations in equilibrium hard-sphere systems; in the sheared case, the discrepancies in magnitudes of distribution peaks are attributable to two interaction effects when pair average trajectories and locations of particles change in response to real, or "hard," and probabilistically favored ("soft") neighboring excluded volumes and, in the case of open triplets, due to changes in the correlation of the farthest separated pair caused by the fixed presence of the particle in the middle.     

Approximation of low rank solutions for linear quadratic control of partial differential equations

Algebraic Riccati equations (ARE) of large dimension arise when using approximations to design controllers for systems modeled by partial differential equations. We use a modified Newton method to solve the ARE that takes advantage of several special features of these problems. The modified Newton method leads to a right-hand side of rank equal to the number of inputs regardless of the weights. Thus, the resulting Lyapunov equation can be more efficiently solved. The Cholesky-ADI algorithm is used to solve the Lyapunov equation resulting at each step. The algorithm is straightforward to code. Performance is illustrated with a number of standard examples. An example on controlling the deflection of the Euler-Bernoulli beam indicates that for weakly damped problems a low rank solution to the ARE may not exist. Further analysis supports this point.