Direct Access to Polyisocyanide Screw Sense Using Vibrational Circular Dichroism


Schwartz, Erik and Domingos, Sergio R. and Vdovin, Alexander and Koepf, Matthieu and Buma, Wybren Jan and Cornelissen, Jeroen J.L.M. and Rowan, Alan E. and Nolte, Roeland J.M. and Woutersen, Sander (2010) Direct Access to Polyisocyanide Screw Sense Using Vibrational Circular Dichroism. Macromolecules, 43 (19). pp. 7931-7935. ISSN 0024-9297

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Abstract:We show that the screw sense of polyisocyanide helices can be determined in a simple manner from the vibrational circular dichroism (VCD) of their CN-stretching mode. The relation between VCD and molecular structure is obtained using the coupled-oscillator approximation. It is shown that since the C═N groups point approximately radially outward from the helical axis, the CN-stretch region of the VCD spectrum of a polyisocyanide helix consists of a single couplet, the sign of which is directly related to the screw sense of the helix. We use this method to determine the screw sense of poly(R)-2-isocyanooctane and poly(S)-2-isocyanooctane from their VCD spectrum.
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Copyright:© 2010 American Chemical Society
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Metis ID: 273728