The exploration of phosphorescent materials based on transition metal-ligand chromophoric complexes represents an important area of research in molecular materials. The knowledge and fundamental understanding of their photophysical properties offer a possible fine-tuning of their electronic absorption and luminescence properties. The strong propensity of d(8) transition metal compounds to form non-covalent metal center dot center dot center dot metal interactions facilitates supramolecular assembly and the formation of supramolecular nanostructures with interesting photophysical properties. The introduction of supramolecular assembly with hierarchical complexity involving non-covalent interactions could lead to research dimensions of unlimited possibilities and opportunities. This article briefly summarizes the latest progress on the use of d(8) metal-ligand chromophores as chemosensors, as exemplified by alkynylplatinum(II) complexes with emphasis on supramolecular assembly involving non-covalent interactions, and the recent advances in the utilization of d(8) metal-ligand phosphors, as exemplified by alkynylgold(III) system, for the exploration and development of phosphorescent OLEDs.