Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 110, Issue 20, Pages 7986-7991Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1301252110
Keywords
chirality; luminescence; noncovalent interactions; platinum complex
Categories
Funding
- University Research Committee (URC) Strategic Research Theme on Molecular Materials
- University Grants Committee Areas of Excellence (AoE) Scheme [AoE/P-03/08]
- Research Grants Council of Hong Kong Special Administrative Region, P. R. China [HKU 7064/11P]
- Hung Hing Ying Scholarship
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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 center dot center dot center dot Pt and pi-pi 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 center dot center dot center dot metal and pi-pi interactions of the alkynylplatinum(II) terpyridine moieties. The folded structure with stabilization via metal center dot center dot center dot metal and pi-pi 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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