The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

New ligands for the Fe(III)‐mediated reverse atom transfer radical polymerization of methyl methacrylate

A series of (di)picolinic acids and their derivates are investigated as novel complexing tridentate or bidentate ligands in the iron‐mediated reverse atom transfer radical polymerization of methyl methacrylate in N,N‐dimethylformamide at 100 °C with 2,2′‐azobisisobutyrontrile as an initiator. The polymerization rates and polydispersity indices (1.32–1.8) of the resulting polymers are dependent on the structures of the ligands employed. Different iron complexes may be involved in iron‐mediated reverse atom transfer radical polymerization, depending on the type of acid used. ¹H NMR spectroscopy has been used to study the structure of the resulting polymers. Chain‐extension reactions have been performed to further confirm the living nature of this catalytic system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2912–2921, 2006     

Nanostructured thermoset epoxy resin templated by an amphiphilic poly(ethylene oxide)‐block‐poly(dimethylsiloxane) diblock copolymer

An amphiphilic poly(ethylene oxide)‐block‐poly(dimethylsiloxane) (PEO–PDMS) diblock copolymer was used to template a bisphenol A type epoxy resin (ER); nanostructured thermoset blends of ER and PEO–PDMS were prepared with 4,4′‐methylenedianiline (MDA) as the curing agent. The phase behavior, crystallization, hydrogen‐bonding interactions, and nanoscale structures were investigated with differential scanning calorimetry, Fourier transform infrared spectroscopy, transmission electron microscopy, and small‐angle X‐ray scattering. The uncured ER was miscible with the poly(ethylene oxide) block of PEO–PDMS, and the uncured blends were not macroscopically phase‐separated. Macroscopic phase separation took place in the MDA‐cured ER/PEO–PDMS blends containing 60–80 wt % PEO–PDMS diblock copolymer. However, the composition‐dependent nanostructures were formed in the cured blends with 10–50 wt % PEO–PDMS, which did not show macroscopic phase separation. The poly(dimethylsiloxane) microdomains with sizes of 10–20 nm were dispersed in a continuous ER‐rich phase; the average distance between the neighboring microdomains was in the range of 20–50 nm. The miscibility between the cured ER and the poly(ethylene oxide) block of PEO–PDMS was ascribed to the favorable hydrogen‐bonding interaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3042–3052, 2006     

The existence of Chern-Simons vortices

A new type of vortices called Chern-Simons vortices is considered and the existence is established.     

A finite model property for RMImin

It is proved that the variety of relevant disjunction lattices has the finite embeddability property. It follows that Avron's relevance logic RMI _min has a strong form of the finite model property, so it has a solvable deducibility problem. This strengthens Avron's result that RMI _min is decidable. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hamiltonian N2‐locally connected claw‐free graphs

A graph G is N₂‐locally connected if for every vertex ν in G, the edges not incident with ν but having at least one end adjacent to ν in G induce a connected graph. In 1990, Ryjá?ek conjectured that every 3‐connected N₂‐locally connected claw‐free graph is Hamiltonian. This conjecture is proved in this note. © 2004 Wiley Periodicals, Inc. J Graph Theory 48: 142–146, 2005     

Crystallization and morphology of poly(vinylidene fluoride)/poly(3‐hydroxybutyrate) blends. I. Spherulitic morphology and growth by polarized microscopy

The development of the poly(3‐hydroxybutyrate) (PHB) morphology in the presence of already existent poly(vinylidene fluoride) (PVDF) spherulites was studied by two‐stage solidification with two separate crystallization temperatures. PVDF formed irregular dendrites at lower temperatures and regular, banded spherulites at elevated temperatures. The transition temperature of the spherulitic morphology from dendrites to regular, banded spherulites increased with increasing PVDF content. A remarkable amount of PHB was included in the PVDF dendrites, whereas PHB was rejected into the remaining melt from the banded spherulites. When PVDF crystallized as banded spherulites, PHB could consequently crystallize only around them, if at all. In contrast, PHB crystallized with a common growth front, starting from a defined site in the interfibrillar regions of volume‐filling PVDF dendrites. It formed by itself dendritic spherulites that included a large number of PVDF spherulites. For blends with a PHB content of more than 80 wt %, for which the PVDF dendrites were not volume‐filling, PHB first formed regular spherulites. Their growth started from outside the PVDF dendrites but could later interpenetrate them, and this made their own morphology dendritic. These PHB spherulites melted stepwise because the lamellae inside the PVDF dendrites melted at a lower temperature than those from outside. This reflected the regularity of the two fractions of the lamellae because that of those inside the dendrites of PVDF was controlled by the intraspherulitic order of PVDF, whereas that from outside was only controlled by the temperature and the melt composition. The described morphologies developed without mutual nucleating efficiency of the components. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 873–882, 2003     

Crystallographic report: catena‐Aqua(2,2′‐bipyrimidine)lithium(I) perchlorate

A lithium(I) coordination polymer has been formed from LiClO₄ and the 2,2′‐bipyrimidine (bpym) ligand in which each square pyramidal lithium(I) atom is coordinated in the basal plane by four nitrogen donor atoms derived from two bpym ligands and one water molecule at the apical position. These are connected into a layer structure via hydrogen‐bonding interactions involving the perchlorate anions. Copyright © 2004 John Wiley & Sons, Ltd.     

A model study for the steady state error of numerical approximations of inviscid flow equations on Cartesian grid

The widely used locally adaptive Cartesian grid methods involve a series of abruptly refined interfaces. In this paper we consider the influence of the refined interfaces on the steady state errors for second‐order three‐point difference approximations of flow equations. Since the various characteristic components of the Euler equations should behave similarly on such grids with regard to refinement‐induced errors, it is sufficient enough to conduct the analysis on a scalar model problem. The error we consider is a global error, different to local truncation error, and reflects the interaction between multiple interfaces. The steady state error will be compared to the errors on smooth refinement grids and on uniform grids. The conclusion seems to support the numerical findings of Yamaleev and Carpenter (J. Comput. Phys. 2002; 181: 280–316) that refinement does not necessarily reduce the numerical error. Copyright © 2005 John Wiley & Sons, Ltd.