Control of Excited-State Supramolecular Assembly Leading to Halide Photorelease

Ground- and excited-state control of halide supramolecular assembly was achieved through the preparation of a series of ester- and amide-functionalized ruthenium polypyridyl complexes in CH₂Cl₂. Hydrogen-bonding amide and alcohol groups on the receptor ligand were found to direct interactions with halide, while halide association with the ethyl ester groups was not observed. The various functional groups on the receptor ligands tuned the ground-state equilibrium constants over 2 orders of magnitude (1 × 10⁵ to 1 × 10⁷ M^-1), and the fractional contribution of each hydrogen-bond donor to the total equilibrium constant was determined. Pulsed-laser excitation of the complexes resulted in excited-state localization on the ester- or amide-functionalized ligands. In the case where the excited state was oriented toward an associated halide ion (the amide complexes), an 80 ± 10 meV Coulombic repulsion was induced that lowered the excited-state equilibrium constant ( K*_eq) and resulted in halide photorelease. The rate constants for excited-state halide release ( k*₂₁) were determined, and the values varied based on the functional groups present in the receptor ligand. Complexes with more hydrogen-bonding donors had smaller rate constants for halide photorelease. In a complex without a specific receptor ligand, the excited-state dipole was not oriented toward the associated halide, and the excited state was therefore found to have a larger equilibrium constant for halide association than the ground state.