Dinuclear coumarin-containing alkynylplatinum() terpyridine complexes with supramolecular assembly-assisted photodimerization

A series of dinuclear coumarin-containing alkynylplatinum( ii ) terpyridine complexes were shown to feature solvent-induced self-assembly behaviors via Pt Pt, π-π stacking, and hydrophobic interactions, displaying drastic color changes from yellow to orange, then to red in solution with the new appe...

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Bibliographic Details
Published in:Materials chemistry frontiers 2023-03, Vol.7 (7), p.1446-1452
Main Authors: Fang, Shishi, Chan, Michael Ho-Yeung, Yam, Vivian Wing-Wah
Format: Article
Language:English
Subjects:
Absorption spectra
Charge transfer
Coumarin
Dimethyl sulfoxide
Hydrophobicity
Ions
Mass spectrometry
Moisture content
NMR spectroscopy
Self-assembly
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Summary:A series of dinuclear coumarin-containing alkynylplatinum( ii ) terpyridine complexes were shown to feature solvent-induced self-assembly behaviors via Pt Pt, π-π stacking, and hydrophobic interactions, displaying drastic color changes from yellow to orange, then to red in solution with the new appearance of a metal-metal-to-ligand charge transfer (MMLCT) absorption band upon increasing the water content in their dimethyl sulfoxide (DMSO) solutions. Photodimerization of the coumarin moieties was found to occur only in the aggregated states with the presence of non-covalent interactions, assisted by the directional Pt Pt interaction, which preorganized the C&z.dbd;C bond of the photo-responsive coumarin moieties in close proximity to each other, enabling topochemical photodimerization upon UV excitation. The aggregation-assisted photodimerization of this series of alkynylplatinum( ii ) terpyridine complexes have been probed by UV-vis absorption spectral changes, 1 H NMR spectroscopy, high-resolution electrospray ionization (ESI)-mass spectrometry and transmission electron microscopy (TEM), demonstrating the role played by supramolecular assembly of the Pt( ii ) complexes in switching on the photodimerization reaction. A series of coumarin-containing alkynylplatinum( ii ) terpyridine complexes features supramolecular-assembly assisted photodimerization, attributed to the preorganized C&z.dbd;C bond of coumarin moieties in close proximity by directional Pt Pt interaction.
ISSN:2052-1537
2052-1537
DOI:10.1039/d2qm01133f