Circular dichroism tensor of a triarylmethyl propeller in sodium chlorate crystals

Yonghong Bing, David Selassie, Ruthanne H. Paradise, Christine Isborn, Nicholas Kramer, Martin Sadilek, Werner Kaminsky, Bart Kahr

Research output: Contribution to journalArticle

Abstract

In 1919, Perucca reported anomalous optical rotatory dispersion from chiral NaClO 3 crystals that were colored by having been grown from a solution containing an equilibrium racemic mixture of a triarylmethane dye (Perucca, E. Nuovo Cimento 1919, 18, 112-154). Perucca s chiroptical observations are apparently consistent with a resolution of the propeller-shaped dye molecules by NaClO 3 crystals. This implies that Perucca achieved the first enantioselective adsorption of a racemic mixture on an inorganic crystal, providing evidence of the resolution of a triarylmethyl propeller compound lacking bulky ortho substituents. Following the earlier report, NaClO 3 crystals dyed with aniline blue are described herein. The rich linear optical properties of (001), (110), and (111) sections of these mixed crystals are described via their absorbance spectra in polarized light as well as images related to linear dichroism, linear birefringence, circular dichroism, and anomalous circular extinction. The linear dichroism fixes the transition electric dipole moments in the aromatic plane with respect to the growth faces of the NaClO 3 cubes. Likewise, circular dichroism measurements of four orientations of aniline blue in NaClO 3 fix a bisignate tensor with respect to the crystal growth faces. Electronic transition moments and circular dichroism tensors were computed ab initio for aniline blue. These calculations, in conjunction with the crystal-optical properties, establish a consistent mixed-crystal model. The nature of the circular extinction depends upon the crystallographic direction along which the crystals are examined. Along 〈100〉, the crystals evidence circular dichroism. Along -110-, the crystals evidence mainly anomalous circular extinction. These two properties, while measured by the differential transmission of left and right circularly polarized light, are easily distinguished in their transformation properties with respect to reorientations of the sample plates. Circular dichroism is symmetric with respect to the wave vector, whereas anomalous circular extinction is antisymmetric. Analysis of Perucca s raw data reveals that he was observing a convolution of linear and circular optical properties. The relatively large circular dichroism should in principle establish the absolute configuration of the propeller-shaped molecules associated with d- or l-NaClO 3 crystals. However, this determination was not as straightforward as it appeared at the outset. In the solid state, unlike in solution, a strong chiroptical response is not in and of itself evidence of enantiomeric resolution. It is shown how it is possible to have a poor resolution - even an equal population of P and M propellers - within a given chiral NaClO 3 crystal and still have a large circular dichroism.

Original languageEnglish (US)
Pages (from-to)7454-7465
Number of pages12
JournalJournal of the American Chemical Society
Volume132
Issue number21
DOIs
StatePublished - Jun 2 2010

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Dichroism
Propellers
Circular Dichroism
Tensors
Sodium
Crystals
Aniline
Coloring Agents
Optical Rotatory Dispersion
Optical properties
Birefringence
Light
Light polarization
Crystallization
sodium chlorate
Adsorption
Dyes
Electric dipole moments
Light extinction
Molecules

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Circular dichroism tensor of a triarylmethyl propeller in sodium chlorate crystals. / Bing, Yonghong; Selassie, David; Paradise, Ruthanne H.; Isborn, Christine; Kramer, Nicholas; Sadilek, Martin; Kaminsky, Werner; Kahr, Bart.

In: Journal of the American Chemical Society, Vol. 132, No. 21, 02.06.2010, p. 7454-7465.

Research output: Contribution to journalArticle

Bing, Y, Selassie, D, Paradise, RH, Isborn, C, Kramer, N, Sadilek, M, Kaminsky, W & Kahr, B 2010, 'Circular dichroism tensor of a triarylmethyl propeller in sodium chlorate crystals', Journal of the American Chemical Society, vol. 132, no. 21, pp. 7454-7465. https://doi.org/10.1021/ja1018892
Bing Y, Selassie D, Paradise RH, Isborn C, Kramer N, Sadilek M et al. Circular dichroism tensor of a triarylmethyl propeller in sodium chlorate crystals. Journal of the American Chemical Society. 2010 Jun 2;132(21):7454-7465. https://doi.org/10.1021/ja1018892
Bing, Yonghong ; Selassie, David ; Paradise, Ruthanne H. ; Isborn, Christine ; Kramer, Nicholas ; Sadilek, Martin ; Kaminsky, Werner ; Kahr, Bart. / Circular dichroism tensor of a triarylmethyl propeller in sodium chlorate crystals. In: Journal of the American Chemical Society. 2010 ; Vol. 132, No. 21. pp. 7454-7465.
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