Ferromagnetic spin alignment in head-to-tail coupled oligo(1, 4-phenyleneethynylene)s and Oligo(1,4-phenylenevinylene)s bearing pendant p-phenylenediamine radical cations

The intramolecular and long-range ferromagnetic coupling between p-phenylenediamine radical cations in head-to-tail coupled oligo(1, 4-phenyleneethynylene)s and oligo(1,4-phenylenvinylene)s between neighbors and next-nearest neighbors is described. UV/vis/near-IR experiments show that the radical cations are localized in the pendant p-phenylenediamine units of the conjugated oligomers. The ESR spectra of these oligo(1,4-phenyleneethynylene) and oligo(1, 4-phenylenvinylene) di(radical cation)s are consistent with those of a triplet state. A linear behavior is observed for the doubly integrated ESR intensity of the DeltaM(s) = +/-1 and DeltaM(s) = +/-2 signals with the inverse temperature (I approximately 1/T), consistent with Curie's law. This behavior indicates a triplet ground-state diradical with a large triplet-singlet energy gap or possibly a degeneracy of singlet and triplet states.     

Near infrared reflectance spectroscopy for the fast identification of PVC-based films

Near infrared (NIR) reflectance spectroscopy was used to develop a non-destructive and rapid qualitative method for the analysis of plastic films used by the pharmaceutical industry for blistering. Three types of films were investigated: 250 microm PVC [poly(vinyl chloride)] films, 250 microm PVC films coated with 40 g m(-2) of PVDC [poly(vinylidene dichloride)] and 250 microm PVC films coated with 5 g m(-2) of TE (Thermoelast) and 90 g m(-2) of PVDC. Three analyses were carried out using different pre-treatment options and a PLS (partial least squares) algorithm. Each analysis was aimed at identifying one type of film and rejecting all types of false sample (different thickness, colour or layer). True and false samples from four plastics manufacturers were included in the calibration sets in order to obtain robust methods that were suitable regardless of the supplier. Specificity was demonstrated by testing validation sets against the methods. The tests showed 0% of type I (false negative identification) and 1% of type II errors (false positive identification) for the PVC method, 13 and 3%, respectively, for the PVC-PVDC method and no error for the PVC-TE-PVDC method. Type II errors, mostly due to the slight sensitivity of the methods to film thickness, are easily corrected by simple thickness measurements. This study demonstrates that NIR spectroscopy is an excellent tool for the identification of PVC-based films. The three methods can be used by the pharmaceutical industry or plastics manufacturers for the quality control of films used in blister packaging.     

Supramolecular phthalocyanine dimers based on the secondary dialkylammonium cation/dibenzo-24-crown-8 recognition motif

[formula: see text] New unsymmetrically substituted DB24C8-phthalocyanines, which are able to form complexes with suitable dialkylammonium cations, have been prepared. These complexes most probably have a pseudorotaxane geometry.     

Low temperature scanning force microscopy of the Si(111)-(7x7) surface

A low temperature scanning force microscope (SFM) operating in a dynamic mode in ultrahigh vacuum was used to study the Si(111)- (7x7) surface at 7.2 K. Not only the twelve adatoms but also the six rest atoms of the unit cell are clearly resolved for the first time with SFM. In addition, the first measurements of the short range chemical bonding forces above specific atomic sites are presented. The data are in good agreement with first principles computations and indicate that the nearest atoms in the tip and sample relax significantly when the tip is within a few A of the surface.