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. 2018 Apr 20;9(18):4253-4257.
doi: 10.1039/c8sc01108g. eCollection 2018 May 14.

Reversible disassembly of metallasupramolecular structures mediated by a metastable-state photoacid

Suzanne M Jansze  1 , Giacomo Cecot  1 , Kay Severin  1
Affiliations

Reversible disassembly of metallasupramolecular structures mediated by a metastable-state photoacid

Suzanne M Jansze et al. Chem Sci. .

Abstract

The addition of a metastable-state photoacid to solutions containing metal-ligand assemblies renders the systems light responsive. Upon irradiation, proton transfer from the photoacid to the ligand is observed, resulting in disassembly of the metallasupramolecular structure. In the dark, the process is fully reversed. Light-induced switching was demonstrated for six different metal-ligand assemblies containing PdII, PtII or RuII complexes and bridging polypyridyl ligands. The methodology allows liberating guest molecules with light.

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Figures

Scheme 1
Scheme 1. Reversible disassembly of metallasupramolecular structures by means of a metastable-state photoacid (PAH). The M6L12 coordination cage is used as a representative example of a metal–ligand assembly.
Scheme 2
Scheme 2. Irradiation with light converts the merocyanine PAH into the spiropyran PA–, with concomitant liberation of a proton.
Scheme 3
Scheme 3. Irradiation of a mixture of complex 1 (125 μM) and the photoacid PAH (8 equiv.) in CD3CN/D2O (8 : 2) by violet light results in the displacement of the pyridyl ligands as evidenced by the 1H NMR (left side) and 31P NMR spectra (right side). The triflate anions of 1 are not shown for clarity. L indicates solvent or OTf–.
Fig. 1
Fig. 1. Structures of the pyridyl ligands A–E.
Fig. 2
Fig. 2. Schematic representation of the metallasupramolecular structures used in this study. Details about the bridging ligands (yellow) are given in ESI.
Scheme 4
Scheme 4. Irradiation of a mixture of cage 5 (10 μM), NaCl (60 μM), and the photoacid PAH (8 equiv. with respect to each bipyridyl ligand) in CD3CN/D2O (8 : 2) by violet light results in disassembly of the cage and liberation of the [B(p-C6H4F)4]– guest (green ball) as evidenced by the 1H NMR (left) and 19F NMR spectra (right). Details about the bridging ligand (yellow) are given in the ESI.
Fig. 3
Fig. 3. Repeated photoswitching between the coordination barrel 8 and its disassembled state. The relative amount of the protonated ligand 8b was used as an indication of the switching efficiency. For the first cycle, the amount of 8b was normalized to 0 and 100%, respectively.
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