Diffusion NMR

High-Boron-Content Porphyrin-Cored Aryl Ether Dendrimers: Controlled Synthesis, Characterization, and Photophysical Properties

The synthesis and characterization of a set of poly(aryl ether) dendrimers with tetraphenylporphyrin as the core and 4, 8, 16, or 32 closo-carborane clusters are described. A regioselective hydrosilylation reaction on the allyl-terminated functions with carboranylsilanes in the presence of Karstedt’s catalyst leads to different generations of boronenriched dendrimers. This versatile approach allows the incorporation of a large number of boron atoms in the dendrimers’ periphery. Translational diffusion coefficients (D) determined by DOSY NMR experiments permit estimation of the hydrodynamic radius (RH) and molecular size for each dendrimer. Furthermore, a notable correlation between D and the molecular weight (MW) is found and can be used to predict their overall size and folding properties. The UV−vis and emission behavior are not largely affected by the functionalization, therefore implying that the presence of carboranes does not alter their photoluminescence properties.