A class of shape-persistent metallodendrimer has been developed through a self-assembly strategy, in which 〈tpy-RuII-tpy〉 or 〈tpy-FeII-tpy〉 connectivity is utilized, as branching moieties or nodes. These metallomacromolecules were fully characterized by 1H and 13C NMR, traveling wave ion mobility mass spectrometry (TWIM MS), single crystal X-ray, UV-vis absorption, photoluminescence, and cyclic voltammetry. Significant increase in the drift times of the same charge states was observed with increasing generation of these complexes, which is in line with the change of molecular size. Moreover, the photophysical properties (molar extinction coefficients) and electrochemical stability of the complexes were noticeably different depending on size and metal ion center.
