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While the ground- and excited-state reduction potentials differ only slightly among the isomers of these complexes, our findings reveal significant variations in the radiative and non-radiative decay rates of the reactivity-controlling triplet 3MLCT states of these closely related species. The observed differences in radiative decay rates could be traced back to variations in the transition dipole moment, vertical energy gaps, and spin\u2013orbit coupling of the isomers. In [Ir(ppy)2(bpy)]+, transition dipole moment differences play a significant role in controlling the relative lifetime of the triplet states, which we rationalized by a vectorial analysis of permanent dipole moments of the ground and excited states. Regarding the two isomers of Ir(ppy)3, changes in radiative decay rates were primarily attributed to variations in vertical energy gaps and intensity borrowing from other singlet-singlet transitions driven by spin\u2013orbit coupling. Non-radiative decay variations were assessed in terms of differences in reorganization energies, adiabatic energy gap, and spin\u2013orbit coupling. For both complexes, reorganization energies associated with low-energy molecular vibrations and metal\u2013ligand bond length changes following the de-excitation process were major contributors. These insights provide a deeper understanding of how molecular design can be leveraged to optimize the performance of iridium-based photoredox catalysts, potentially guiding the development of more efficient catalytic systems for future applications.<\/jats:p>","DOI":"10.1063\/5.0239293","type":"journal-article","created":{"date-parts":[[2025,1,14]],"date-time":"2025-01-14T12:20:31Z","timestamp":1736857231000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":2,"title":["A computational study on the effect of structural isomerism on the excited state lifetime and redox energetics of archetype iridium photoredox catalyst platforms [Ir(ppy)2(bpy)]+ and Ir(ppy)3"],"prefix":"10.1063","volume":"162","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8439-3141","authenticated-orcid":false,"given":"Daniel","family":"G\u00f3mez Bustos","sequence":"first","affiliation":[{"name":"Department of Chemistry and Biochemistry, University of Texas at El Paso , El Paso, Texas 79968,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5728-0512","authenticated-orcid":false,"given":"Sreeprasad","family":"Sreenivasan","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry, University of Texas at El Paso , El Paso, Texas 79968,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0051-5229","authenticated-orcid":false,"given":"Balazs","family":"Pinter","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry, University of Texas at El Paso , El Paso, Texas 79968,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2025,1,14]]},"reference":[{"key":"2025011412202488700_c1","doi-asserted-by":"publisher","first-page":"213293","DOI":"10.1016\/j.ccr.2020.213293","article-title":"A trip in the nonlinear optical properties of iridium complexes","volume":"414","year":"2020","journal-title":"Coord. 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