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Ligand Control of Supramolecular Chloride Photorelease.
Inorganic Chemistry 2018 May 8
Supramolecular assembly is shown to provide control over excited-state chloride release. Two dicationic chromophores were designed with a ligand that recognizes halide ions in CH2 Cl2 and a luminescent excited state whose dipole was directed toward, 12+ , or away, 22+ , from an associated chloride ion. The dipole orientation had little influence on the ground-state equilibrium constant, Keq ∼ 4 × 106 M-1 , but induced a profound change in the excited-state equilibrium. Light excitation of [12+ ,Cl- ]+ resulted in time-dependent shifts in the photoluminescence spectra with the appearance of biexponential kinetics consistent with the photorelease of Cl- . Remarkably, the excited-state equilibrium constant was lowered by a factor of 20 and resulted in nearly 45% dissociation of chloride. In contrast, light excitation of [22+ ,Cl- ]+ revealed a 45-fold increase in the excited-state equilibrium constant. The data show that rational design and supramolecular assembly enables the detection and photorelease of chloride ions with the potential for future applications in biology and chemistry.
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