In this work, we report the design and photophysical properties of a unique class of Ni porphyrins, in which the tert-butyl benzene substituents at the meso positions of the macrocycle were tethered by ethers with alkyl linkers. This not only results in the permanently locked ruf distortion of the macrocycle but also enables the engineering of the degree of distortion through varying the length of alkyl linkers, which addressed the complication of uncertainty in the specific structural

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... ns that has long plagued the porphyrin photophysical community. Using advanced time-resolved optical and X-ray absorption spectroscopy, we observed tunability in the excited-state relaxation pathway depending on the degree of distortion and characterized the associated transient intermediate structure. These findings provide a new avenue to afford accessibility to a wide range of excited-state properties in nonplanar porphyrins.