Polyarene dendrimers with rigid aromatic regions are of interest due to their shape persistent nature. A novel series of G1 dendrimers containing a substituted 1,3-phenyl core are reported and were found to exhibit atropisomerism. This was investigated in the solid state (X ray), in solution (NMR), and via computational studies. The synthesis of fluorinated G1 dendrimers allowed for the analysis of interconversion between conformations via 19F-19F EXSY NMR (exchange spectroscopy). These were shown to exist as two distinct sets of three interconverting atropisomers. Each atropisomer was identified as well as their respective interconversion pathway. By increasing the size of the core of the G1 dendrimers resulted in physical separation of atropisomers by preparative HPLC. Results suggest certain conformers are energetically unfavourable reducing the total number of atropisomers observed.