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arXiv · 2311.01704

Test of the Orbital-Based LI3 Index as a Predictor of the Height of the $^3$MLCT $\rightarrow$ $^3$MC Transition-State Barrier for Gas-Phase [Ru(N$^\wedge$N)$_3$]$^{2+}$ Polypyridine Complexes

Denis Magero·Ala Aldin M. H. M. Darghouth·Mark E. Casida
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Abstract

Luminescence lifetimes of Ruthenium (II) polypyridine compounds is thought to be controlled by the barrier to conversion of triplet metal-ligand charge transfer ($^{3}$MLCT) state to a non-luminescent triplet metal-centered ($^{3}$MC) state. This work builds on earlier work [J. Photochem. Photobiol. A 276, 8 (2014)] and [J. Photochem. Photobiol. A 348, 305 (2017)] that derived several orbital-based luminescence indices of which the third (LI3) was based upon frontier-molecular-orbital-like ideas and correlated linearly with values of $E_{ave}$. $E_{ave}$ is a large underestimate of the true $^3$MLCT$\rightarrow$ $^3$MC TS barrier height in the case of the tris bipyridine ruthenium(II) cation {[Ru(bpy)$_3]^{2+}$}, but accurate TS barrier heights are difficult to obtain experimentally, it was judged useful to verify the ideas used to derive the LI3 index by calculating the energetics of the gas-phase $^{3}$MLCT $\rightarrow$ $^{3}$MC reaction for four complexes $\{$[Ru(N$^\wedge$N)$_3$]$^{2+}$ with N$^\wedge$N = bpy ({6}), 4,4'-dm-bpy ({70}), 4,4'-dph-bpy ({73}), and 4,4'-DTB-bpy ({74}) $\}$ using the same density functional and basis sets used in calculating LI3. We examine the trans dissociation mechanism in detail at the B3LYP/6-31G+LANLDZ(Ru) level and uncover a two-part mechanism. In the first part, the electron is transferred to a single ligand rather than symmetrically to all three ligands. It is the two Ru-N bonds to this ligand which are equally elongated in the transition state. The intrinsic reaction coordinate then continues down a ridge in hyperspace and bifurcates into one of two symmetry-equivalent $^3$MC structures with elongated trans bonds. Interestingly, no significant difference is found for the TS barriers for the four complexes treated here. Instead, LI3 is linearly correlated with the energy difference $\Delta$ E = E($^{3}$MLCT) - E($^{3}$MC).

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Denis Magero, Ala Aldin M. H. M. Darghouth, Mark E. Casida. 2023-11-03. Test of the Orbital-Based LI3 Index as a Predictor of the Height of the $^3$MLCT $\rightarrow$ $^3$MC Transition-State Barrier for Gas-Phase [Ru(N$^\wedge$N)$_3$]$^{2+}$ Polypyridine Complexes. https://arxiv.org/abs/2311.01704

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