Tetra-arylporphyrins constitute appealing molecular platforms endowed with interesting linear and nonlinear optical properties. In particular, when associated to electron-rich alkynyl complexes, the resulting molecules can present remarkable properties for developing molecular-based devices for electronics or photonics,[1] such as for instance redox-switchable fluorophores[2] or electrochromic NLO-phores[3]. We will first recall how recent studies on well-designed molecular model such as M1-3 allowed us to reach a better understanding of the role of the particular [Ru(dppe)2Cl] alkynyl unit on the photonic properties, at the molecular level,[4] before showing how this knowledge can be used to build porphyrin-based nonlinear chromophores such as 1-2a-b that might present an applied potential in the field of anti-cancerous phototherapy.