Chromophore arrays based on rigid dendritic, hyperbranched and tetrahedrally branched architectures

9-Phenylcarbazole ethynylene monodenrons were prepared using three different peripheral groups creating well-organized arrays of redox centers. Solubility of the monodendrons was found to be dependent on the peripheral groups. Only three generations of monodendrons with tert-butyl and 1,1,3,3-tetramethyl-butyl peripheral groups were realized due to difficulties in the purification of mondendron 31-mer. A peripheral monomer with two 3,5-di-tert-butyl-4-(2-methoxy-ethoxy)-phenylene groups at the 3,6-positions of carbazole increases the solubility as well as the polarity of the monodendrons so as to facilitate the separation by adsorption chromatography and monodendrons up to generation four (MW = 16.6 kDa) were realized. A monomer bearing a 3-hydroxy-3-methyl-but-1-ynyl group at its focal point as a masking group for terminal acetylene functionality was used to facilitate the removal of diacetylene byproducts. Carbon disulfide, a solvent of high polarizability, was found to be a good solvent for all the monodendrons. Spectroscopic studies showed limited through-bond conjugation over the monodendrons and long-range through-space interactions in larger molecules. Light energy absorbed by 9-phenylcarbazole monodendrons can be efficiently transferred to a suitable acceptor chromophore such as perylene that is positioned at the focal point. Photoinduced electron transfer may occur when a suitable electron acceptor, (e.g. 3,5-dicyanobenze) is attached to the focal point.; 9-Phenylcarbazole hyperbranched polymers with appreciable molecular weight (20-30 kDa) and low polydispersities were prepared using a slow monomer addition procedure. Adsorption chromatography can be effectively employed to fractionate these polymers when the polar 3,5-di-tert-butyl-4-(2-methoxyethoxy)-phenylene groups are placed at the periphery. By using fluorescent or electron-accepting focal point groups, potential luminescent or photoconductive materials can be prepared. Average molecular weight can be controlled by varying the monomer: core ratio.; Phenylacetylene monodendrons with 9-phenylcarbazoles at the periphery were synthesized using a monomer containing a polar silane masking-group for the terminal acetylene functionality. When a perylene was attached to the focal point of these monodendrons, light energy absorbed by the peripheral 9-phenylcarbazoles can be efficiently transferred across the phenylacetylene segments to perylene.; Two tetrapodal structures containing four rigid arms incorporating anthracene chromophores were synthesized. Amorphous and luminescent properties of these compounds were characterized by thermal analysis and fluorescence spectroscopy.