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. Author manuscript; available in PMC: 2020 May 21.
Published in final edited form as: J Am Chem Soc. 2019 Jun 27;141(27):10777–10787. doi: 10.1021/jacs.9b04303

Figure 2.

Figure 2.

Comparison of the DFT-computed internal reaction coordinates and transition states for intramolecular PT in Flr(H)CO2− (A, C, and E) and for the MS-CPET reaction of Flr(H)CO2− and N(ArBr)3•+ (B, D, and F). (A and B) The transition state occurs at x = 0 along the reaction coordinate. Proceeding to negative values along the x-axis leads toward reactants, while proceeding to positive values leads to products. Black “○” show potential energy (ΔE) along the reaction coordinate. (C and D) Red “□” show the distance between the fluorenyl proton and the carboxylate oxygen along the reaction coordinate, which is a measure of proton transfer. For intramolecular PT, the fluorenyl proton has proceeded 76% toward the carboxylate oxygen. For MS-CPET, the fluorenyl proton has proceeded 44% toward the carboxylate oxygen. (E and F) Blue “Δ” show the sum of the CCC bond angles along the fluorenyl carbon along the reaction coordinate, which is a measure of electronic reorganization. For intramolecular PT, the sum of the fluorenyl CCC bond angles has proceeded 45% toward the final geometry. For MS-CPET, the sum of the fluorenyl CCC bond angles has proceeded 29% toward the final geometry.