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J Am Chem Soc. 2008 Dec 10;130(49):16812-22. doi: 10.1021/ja806723e.

Dendritic molecular switch: chiral folding and helicity inversion.

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  • 1Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, USA.

Erratum in

  • J Am Chem Soc. 2009 Oct 28;131(42):15564.

Abstract

Appropriately designed chemical architectures can fold to adopt well-defined secondary structures without the need for structural motifs of biological origin. We have designed tris(N-salicylideneaniline)-based hyperbranched molecules that spontaneously collapse to compact three-blade propeller geometry of either (P)- or (M)-handedness. For a homologous series of compounds, a direct correlation was established between the absolute screw sense, either (P)- or (M)-, of this helical folding and the absolute configuration, either (R)- or (S)-, of the chiral alcohol groups introducing local asymmetric bias to the conformationally restricted molecular backbone. 1H NMR and CD spectroscopic studies provided significant insights into structural folding and unfolding of these chiral molecules in solution, which proceed via reversible assembly and disassembly of the C3-symmetric hydrogen-bonding network. Notably, solvents profoundly influenced this dynamic process. A strong correlation between the solvent donor number (DN) or solvent basicity (SB) parameters and the change in the Cotton effects pointed toward specific O-H...solvent interactions that drive structural unfolding and eventual refolding to apparently opposite helicity. This unusual chirality inversion process could also be induced by installation of chemical protecting groups that simulate specific solvent-solute interactions. Removal of this covalent mimic of the solvent shell restored the original screw sense of the parent molecule, thus establishing the feasibility of covalently triggered helicity inversion as a new mode of operation for chiroptical molecular switches.

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