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Supramolecular complexes of a poly(tert-butoxystyrene)-block-polystyrene-block-poly(4-vinylpyridine) triblock copolymers and less than stoichiometric amounts of pentadecylphenol (PDP) are shown to self-assemble into a core-shell gyroid morphology with the core channels formed by the hydrogen-bonded P4VP(PDP)complexes. After structure formation, PDP was removed using a simple washing procedure, resulting in well-ordered nanoporous films that were used as templates for nickel plating.

b-P4VP) linear triblock copolymers, with the P4VP weight fraction varying from 0.08 to 0.39, were synthesized via sequential anionic polymerization. The values of the unknown interaction parameters between styrene and tert-butoxystyrene and between tert-butoxystyrene and 4-vinylpyridine were determined from random copolymer blend miscibility studies and found to satisfy 0.031 < χ S,tBOS < 0.034 and 0.39 < χ 4VP,tBOS <0.43, the latter being slightly larger than the known 0.30 < χ S,4VP e 0.35 value range. All triblock copolymers synthesized adopted a P4VP/PS core/shell cylindrical self-assembled morphology. From these four triblock copolymers supramolecular complexes were prepared by hydrogen bonding a stoichiometric amount of pentadecylphenol (PDP) to the P4VP blocks. Three of these complexes formed a triple lamellar ordered state with additional short length scale ordering inside the P4VP(PDP) layers. The self-assembled state of the supramolecular complex based on the triblock copolymer with the largest fraction of P4VP consisted of alternating layers of PtBOS and P4VP(PDP) layers with PS cylinders inside the latter layers. The difference in morphology between the triblock copolymers and the supramolecular complexes is due to two effects: (i) a change in effective composition and, (ii) a reduction in interfacial tension between the PS and P4VP containing domains. The small angle X-ray scattering patterns of the supramolecules systems are very temperature sensitive. A striking feature is the disappearance of the first order scattering peak of the triple lamellar state in certain temperature intervals, while the higher order peaks (including the third order) remain. This is argued to be due to the thermal sensitivity of the hydrogen bonding and thus directly related to the very nature of these systems.

A series of N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (TOEEDH4) ligand precursors and their group 4 metal complexes have been prepared. The complexes have been characterized by single-crystal X-ray diffraction and (1)H NMR spectroscopy, highlighting the ability to systematically vary the number of TOEED ligands within the system. Initial catalytic data for the solvent-free, ring-opening polymerization of rac-lactide (rac-LA), a promising degradable polymer produced from renewable resources, is reported. At 135 °C, it has been demonstrated that the activity of the complexes is enhanced by increasing the number of labile isopropoxide groups. When the temperature was further increased to 165 °C, all complexes demonstrated a far higher activity irrespective of the identity of the metal or number of labile initiator groups. Polymerization kinetics were monitored in real time using FT-IR spectroscopy with a diamond composite insertion probe and Ti4(TOEED)(O(i)Pr)12 was demonstrated to convert over 95% of the rac-LA within 160 min.