The dissertation covers three major topics: metal-assisted aromaticity, synthetic approaches to tailor donor-acceptor supramolecular stacks, and photoluminescence properties of cyclic trinuclear complexes (CTCs) of d10 metals. First, multiple theoretical approaches are adapted to discuss in detail the origin of aromaticity of CTCs, putting forward a metal-assisted aromaticity model. Next are the discoveries of donor-acceptor stacked CTC–CTC' complexes from both experimental and computational perspectives, reporting multiple novel crystallography-determined structures and revealing their pertinent intermolecular ground-state charge transfer. The spontaneous binding behavior is also determined by UV-vis and NMR titrations and rationalized as the cooperation of multiple supramolecular interactions, including metallophilicity, electrostatic attraction, and dispersion. The last part includes systematic investigations of photoluminescence properties of halogen-metal-bonded CTCs and sandwich-like cation–π-bonded heptanuclear clusters based on CTCs. The cooperative effects of metal-centered conformation, the heavy-atom and relativistic effects from both the halogen and metal atoms play complementary roles in the phosphorescence process to promote the inter-system crossing and radiative transitions.