Dynamic scaffold of chiral binaphthol derivatives with the alkynylplatinum(II) terpyridine moiety.
نویسندگان
چکیده
Platinum(II)-containing complexes with inherently chiral binaphthol derivatives display a versatile scaffold between random coils and single-turn helical strands, in which the conformational transition is controlled by the Pt···Pt and π-π interactions of alkynylplatinum(II) terpyridine moiety upon solvent and temperature modulation. The bisignate Cotton effect in the circular dichroism spectra is indicative of the cooperative transformation from random coil state to a compact single-turn M- or P-helix. More importantly, as revealed by the appearance of new UV-vis absorption and emission bands during conformational change, the self-assembly of the platinum(II)-containing complex into a helical structure is assisted by the metal···metal and π-π interactions of the alkynylplatinum(II) terpyridine moieties. The folded structure with stabilization via metal···metal and π-π interactions has been supported by density functional theory calculations, which provide insights into the folded geometry of these kind of metallo-foldamers.
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A new class of platinum(II) terpyridine complexes with a phosphole-derived bridging alkynyl ligand have been prepared. The X-ray crystal structure of complex 2 has been determined, and reveals a polymeric zig-zag chain structure with the existence of p–p stacking interactions. The photophysical properties have also been studied, with MLCT/LLCT phosphorescence exhibited in degassed CH2Cl2; the e...
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ورودعنوان ژورنال:
- Proceedings of the National Academy of Sciences of the United States of America
دوره 110 20 شماره
صفحات -
تاریخ انتشار 2013