9810283 Hogen-Esch At low degrees af polymerization (DP< 30) the pendent phenyl groups of macrocyclic polystyrene are known to organize in parallel fashion leading to increased absorptivity (hyperchromicity) and strongly (six times) enhanced excimer fluorescence. The synthesis is proposed (by anionic polymerization followed by high dilution coupling) of analogous macrocyclic vinyl polymers such as macrocyclic polyvinylnaphthalene containing single photochemical acceptors such anthracene or pyrene. Such polymers are expected to be capable of strongly enhanced absorptivity and efficient Foster transfer to the photochemical acceptor. The enhanced absorptivity and luminescence of the above macrocycles will be applied to the synthesis of macrocyclic photon harvesting antenna type polymers containing a peripherally positioned acceptor chromophore the orientation of which with respect to the parallel set of pendent donors, is systematically optimized to allow highly efficient donor- donor and donor- acceptor coupling. Thus the key issue that will receive attention will be the optimization of donor-donor and donor-acceptor orientation with respect to the quantum yield of conversion of incident light. The donors and acceptor combinations will be those that have been well studied in other types of antenna polymers such as linear- random or block copolymers of donor and acceptors, or photozymes, dendrimers incorporating donor - acceptor combinations etc., so that comparisons with a variety of alternative structures are possible. The acceptors to be included into the PS macrocycles through incorporation into the coupling agent will include naphthalenes incorporated through the 1,2- 2,3- or 2,6- positions. Acceptors in the proposed polyvinylnaphthalenes will include anthracenes, pyrenes and similar chromophores the incorporation of which also will be subject to a systematic change in orientation with regard to the donor chromophores. The extent of donor-do nor energy migration and donor- acceptor singlet transfer in the macrocycles and in the macrocyclic antenna polymers will be studied by steady state and time resolved luminescence measurements at ambient temperatures and in low temperature glasses using both circularly- and plane-polarized light. %%% These polymers are of potential interest in efficient light emitting- and in optical power limiting devices and in upconversion lasing of photovoltaics. The possible similarity to chrorophyll assemblies is striking and will be explored. ***
