The formation of nanostructures in triblock terpolymers consisting of poly[2-ethyl-2-oxazoline-block-2-(1-ethylpentyl)-2-oxazoline-block-2-(Xfluorophenyl)-2-oxazoline] (X ¼ di, tri, tetra and penta) was investigated in water. For this purpose a gradually increasing degree of fluorination was introduced in the molecular structures and its influence on the self-assembly was studied. It can be demonstrated that the basic form of aggregation of these systems resembles rod-like micelles, which tend, upon introduction of fluorinated blocks, to aggregate first into 2-dimensional and later into 3-dimensional super-aggregates. In the case of di-and pentafluorinated terpolymers well-defined structures were observed, which represent likely intermediate, stable transient structures formed during an assumed rod-to-vesicle transition. DLS and cryo-TEM were utilized to analyze the structural features of these nanostructures and a model for their further assembly into super-structures was developed.

Supramolecular assemblies involving interaction of a small organic molecule, 2-hydroxy-6-Naphthoic acid (HNA), with poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymers are utilized to obtain micellar structures in solution, nanostructured thin films on flat substrates and, finally, nanoporous thin films. The formation of hydrogen bonds between HNA and the poly(4-vinylpyridine) (P4VP) blocks is confirmed by spectroscopic measurements. The accordingly P4VP/HNA hydrogen-bonded complexes are poorly soluble in 1,4-dioxane, resulting in the formation of micellar structures with a P4VP/HNA core and a polystyrene (PS) corona. Those micelles have been spin-coated onto silicon wafers, resulting in nanostructured thin films consisting of P4VP/HNA dot-like features embedded in a PS matrix. The morphology of those films has been tuned by solvent annealing. Selective dissolution of HNA by methanol results in the formation of a nanoporous thin film. The P4VP/HNA nanodomains have been also cross-linked by borax, and the thin films have been further dissolved in a good solvent for PS, leading to micelles with a structure reminiscent of the thin films.

The one-pot synthesis of useful [Pt 2 (0)(η 4 -1,6-diene) 3 ] complexes, directly from H 2 PtCl 6 ‚xH 2 O, has remained an unaddressed problem. We haVe found that the treatment of an i-PrOH solution of H 2 PtCl 6 ‚xH 2 O by (Me 3 SiO) 2 MeSi(CHdCH 2 ), in the presence of allyl ether (AE), followed by reaction of the in situ generated Pt(0) species with IPr carbene (IPr ) 1,3bis(2,6-diisopropylphenyl)imidazol-2-ylidene) enables the isolation of (IPr)Pt(AE) (1) in 50-70% yield. The scope of this method has been extended to other (L)Pt(1,6-diene) complexes (L ) 1,3-dicyclohexylimidazol-2-ylidene, triphenylphoshine; 1,6diene ) diethyl 2,2-diallylmalonate (DAM)), and the molecular structure of the (IPr)Pt(DAM) (4) complex has been unequiVocally determined by a single-crystal X-ray diffraction analysis. These results are significant for the formation of actiVe L-Pt-(0) fragments in catalysis.