Hyperbranched and monodispersed tree-like macromolecules that are commonly referred to as dendrimers [1][2][3][4][5][6] have been attracting tremendous attention due to their significant potential in designing novel materials for applications in material science, medicine, and catalysis. Dendrimers (Fig. 5.1) can be synthesized using two different iterative step-by-step synthetic methodologies: (1) a divergent approach that starts from a plurifunctional core and extends outward in a layer-by-layer fashion, as initially described by V€ ogtle and coworkers [7] and subsequently extended by Tomalia et al. [8] or (2) alternatively, using a less common convergent strategy that involves grafting dendrons onto the core [9][10][11].The flurry of activity that followed these initial reports has generated a wealth of these macromolecules [12], and much emphasis has subsequently shifted to understanding their structure-property relationships, and then, applying these principles to design goaloriented applications. In addition, during the past few years, intriguing fluorescence properties offered by dendrimers have been studied in detail, and have been extended to a wide range of applications such as light harvesting [13][14][15], two-photon absorption [16,17], labeling agents for biology [18][19][20][21], and in the design of efficient and competitive OLEDs [22][23][24][25]. Furthermore, investigations regarding dendrimers and their interactions with metals have also expanded at a fast pace. Metallodendrimers [4,[26][27][28], as they are generally called, are now an integral part of the main-stream dendritic macromolecules. Thesewell-defined architectures include metal complexes of varied forms as illustrated in Fig. 5.2. Metallodendrimers can be synthesized using a stepwisebuild-upapproachinwhichcoordination ligands bindtometals ofawidevariety that can be placed at the core, the periphery, and even as divergent points or a combination