In this work, multi-technique probing with transient optical absorption spectroscopy (tr-OAS) and transient X-ray emission spectroscopy (tr-XES) are combined with Full-dimensional Trajectory Surface Hopping (TSH) dynamics simulations to establish a clear correlation between CT and bifurcation in the excited state landscape of a prototypical Ni(II) porphyrin (NiP). Based on these results, NiPs and other open-shell MPs are now placed on the roadmap that charts the development of low-Z sensitizers as a templating platform of hot CT chromophores optimized for boosting endergonic photoconversion schemes.