Giant Dielectric Permittivity of Electron-Doped Manganite Thin Films, Ca(1-x)La(x)MnO(3) ($0<= x<= 0.03)

A giant low-frequency, in-plane dielectric constant, eps~10^6, for epitaxial thin films of Ca(1-x)La(x)MnO(3) (x<=0.03) was observed over a broad temperature range, 4K <= T 300K. This phenomenon is attributed to an internal barrier-layer capacitor (IBLC) structure, with insulating boundaries between semiconducting grains. The room-temperature eps increases substantially with electron (La) doping. The measured values of eps exceed those of conventional two-phase IBLC materials based on (Ba,Sr)TiO(3) as well as recently discovered CaCu(3)Ti(4)O(12) and (Li,Ti) doped NiO.Comment: 5 pages, 4 fig.s, J. Appl. Phys., Jan. 15, 2005 (in press

Low-Temperature Permittivity of Insulating Perovskite Manganites

Measurements of the low-frequency (f<=100 kHz) permittivity and conductivity at T<= 150 K are reported for La(1-x)Ca(x)MnO(3) (0<=x<=1) and Ca(1-y)Sr(y)MnO(3) (0<=y<=0.75) having antiferromagnetic, insulating ground states covering a broad range of Mn valencies from Mn(3+) to Mn(4+). Static dielectric constants are determined from the low-T limiting behavior. With increasing T, relaxation peaks associated with charge-carrier hopping are observed in the real part of the permittivities and analyzed to determine dopant binding energies. The data are consistent with a simple model of hydrogenic impurity levels and imply effective masses m*/m_e~3 for the Mn(4+) compounds. Particularly interesting is a large dielectric constant (~100) associated with the C-type antiferromagnetic state near the composition La(0.2)Ca(0.8)MnO(3).Comment: 6 pages, 8 figures, PRB in pres

Increasing 3D Supramolecular Order by Decreasing Molecular Order. A Comparative Study of Helical Assemblies of Dendronized Nonchlorinated and Tetrachlorinated Perylene Bisimides

A nonplanar, twisted, and flexible tetrachlorinated perylene bisimide (Cl4PBI) was functionalized with two AB3 minidendrons containing hydrogenated or semifluorinated dodecyl groups. The hydrogenated dendron was attached to the imide groups of Cl4PBI via m = 0, 1, and 2 methylenic units, whereas the dendron containing semifluorinated groups was attached via m = 3 or a di(ethylene oxide) linker (m = 2EO). The supramolecular structures of these compounds, determined by a combination of differential scanning calorimetry, X-ray diffraction, and solid-state NMR, were compared with those of nonchlorinated planar and rigid PBI reported previously, which demonstrated the thermodynamically controlled formation of 2D periodic arrays at high temperatures and 3D arrays at low temperatures. The molecularly less ordered Cl4PBI containing hydrogenated dendrons self-organize into exclusively 3D crystalline periodic arrays under thermodynamic control for m = 0 and 2, while the more highly molecularly ordered PBI produced less stable and ordered 3D crystals and also 2D assemblies. This induction of a higher degree of 3D order in supramolecular assemblies of the less well-ordered molecular building blocks was unanticipated. The semifluorinated dendronized Cl4PBI with m = 3 formed a 2D columnar hexagonal array under kinetic control, whereas the compound with m = 2EO formed an unusual 2D honeycomb-like hexagonal phase under thermodynamic control. These Cl4PBI compounds provide a new route to stable crystalline assemblies via thermodynamic control at lower temperatures than previously obtained with PBI, thus generating 3D order in an accessible range of temperature of interest for structural analysis and for technological applications

Četrdeset godina rada i razvoja Vojnogeografskog instituta u socijalističkoj Jugoslaviji

U članku je dan pregled četrdesetogodišnjeg rada i razvoja Vojnogeografskog instituta u socijalističkoj Jugoslaviji

A supramolecular helix that disregards chirality

The functions of complex crystalline systems derived from supramolecular biological and non-biological assemblies typically emerge from homochiral programmed primary structures via first principles involving secondary, tertiary and quaternary structures. In contrast, heterochiral and racemic compounds yield disordered crystals, amorphous solids or liquids. Here, we report the self-assembly of perylene bisimide derivatives in a supramolecular helix that in turn self-organizes in columnar hexagonal crystalline domains regardless of the enantiomeric purity of the perylene bisimide. We show that both homochiral and racemic perylene bisimide compounds, including a mixture of 21 diastereomers that cannot be deracemized at the molecular level, self-organize to form single-handed helical assemblies with identical single-crystal-like order. We propose that this high crystalline order is generated via a cogwheel mechanism that disregards the chirality of the self-assembling building blocks. We anticipate that this mechanism will facilitate access to previously inaccessible complex crystalline systems from racemic and homochiral building blocks

Induction of the Columnar Phase of Unconventional Dendrimers by Breaking the C2 Symmetry of Molecules

[[abstract]]Two triazine-based unconventional dendrimers were prepared and characterized by 1H and 13C NMR spectroscopy, mass spectrometry, and elemental analysis. Differential scanning calorimetry, polarizing microscopy, and powder XRD studies showed that these dendrimers display columnar liquid-crystalline phases during thermal treatment. This is ascribable to breaking of their C2 symmetry. The molecular conformations of prepared dendrimers were obtained by computer simulation with the MM3 model of the CaChe program in the gas phase. The simulation showed that the conformations of the prepared dendrimers are rather flat and disfavor formation of the LC phase. However, due to C2-symmetry breaking, the prepared dendrimers have structural isomers in the solid state and thus show the desired columnar phases. This new strategy should be applicable to other types of unconventional dendrimers with rigid frameworks.[[journaltype]]國外[[incitationindex]]SCI[[ispeerreviewed]]Y[[booktype]]電子版[[booktype]]紙本[[countrycodes]]DE