Ligand Control of Supramolecular Chloride Photorelease
(2018) Inorganic Chemistry — Vol. 57, n° 9, p. 5624-5631 (2018)
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- Authors
Sampaio, Renato N. 
Meyer, Gerald J.
- Abstract
- 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 CH2Cl2 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.
- Affiliations
Citations
Turlington, M. D., Troian-Gautier, L., Sampaio, R. N., Beauvilliers, E. E., & Meyer, G. J. (2018). Ligand Control of Supramolecular Chloride Photorelease. Inorganic Chemistry, 57(9), 5624-5631. https://doi.org/10.1021/acs.inorgchem.8b00559 (Original work published 2018)