A series of platinum(II) bipyridine complexes with two rhodamine-like alkynyl (Rhodyne) ligands were developed to show chemo-induced "ON-OFF" switching capabilities with exceptional near-infrared phosphorescence and delayed fluorescence. This study contributes to the design of versatile photosensitizers with multiple functionalities, including metal ion and biomolecule sensing, photodynamic therapy, and optoelectronics.