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Raman Microspectrometry as a New Approach to the Investigation of Molecular Recognition in Solids: Chloroform−Cryptophane Complexes
- Source :
- Journal of Physical Chemistry B, Journal of Physical Chemistry B, American Chemical Society, 2004, 108 (18), pp.5572-5581. ⟨10.1021/jp0375158⟩, The Journal of physical chemistry, The Journal of physical chemistry, 2004, 108, pp.5572-5581. ⟨10.1021/jp0375158S1089-5647(03)07515-1⟩, The Journal of physical chemistry, American Chemical Society (ACS), 2004, 108, pp.5572-5581. ⟨10.1021/jp0375158S1089-5647(03)07515-1⟩, Journal of Physical Chemistry B, 2004, 108 (18), pp.5572-5581. ⟨10.1021/jp0375158⟩
- Publication Year :
- 2004
- Publisher :
- HAL CCSD, 2004.
-
Abstract
- Information about the orientation and dynamics of a chloroform molecule encaged in cryptophane-A and cryptophane-E is obtained by means of Raman microspectrometry. The microscopy technique allows us to study the two observed crystalline structures of the CDCl 3 -cryptophane-A complexes separately. The spectra, recorded under different polarization conditions, are compared with those of CHCl 3 -D 3 0 -cryptophane-A and analyzed in light of the crystalline structures determined by X-ray diffraction. The spectral analysis is improved by ab initio calculations performed for the isolated guest and host molecules. The orientation of the encaged chloroform with the C-H bond pointing toward the center of the cyclotriveratrylene structures is confirmed. The vCD (or vCH) stretching wavenumber of chloroform is red shifted upon complexation as compared to the wavenumber of the gaseous isolated state. This red shift, larger for the CDCl 3 -cryptophane-E complex than for the CDCl 3 -cryptophane-A complex, is the signature of stronger binding host-guest interactions with cryptophane-E. In addition, the analysis of the band shape of the vCD stretching vibration of chloroform suggests different rotational dynamics for the guest molecule encaged in cryptophane-A or in cryptophane-E. This work illustrates the capability of the Raman microspectrometry technique to investigate molecular recognition phenomena in solids.
- Subjects :
- host-guest interactions
Cyclotriveratrylene
010402 general chemistry
01 natural sciences
Spectral line
Cryptophane
chemistry.chemical_compound
symbols.namesake
Raman microspectrometry
Molecular recognition
Ab initio quantum chemistry methods
Computational chemistry
Materials Chemistry
Molecule
[CHIM]Chemical Sciences
cryptophane
Physical and Theoretical Chemistry
ComputingMilieux_MISCELLANEOUS
Chloroform
010405 organic chemistry
ab initio calculations
0104 chemical sciences
Surfaces, Coatings and Films
Crystallography
chemistry
symbols
Raman spectroscopy
Subjects
Details
- Language :
- English
- ISSN :
- 15206106, 15205207, 00223654, and 15415740
- Database :
- OpenAIRE
- Journal :
- Journal of Physical Chemistry B, Journal of Physical Chemistry B, American Chemical Society, 2004, 108 (18), pp.5572-5581. ⟨10.1021/jp0375158⟩, The Journal of physical chemistry, The Journal of physical chemistry, 2004, 108, pp.5572-5581. ⟨10.1021/jp0375158S1089-5647(03)07515-1⟩, The Journal of physical chemistry, American Chemical Society (ACS), 2004, 108, pp.5572-5581. ⟨10.1021/jp0375158S1089-5647(03)07515-1⟩, Journal of Physical Chemistry B, 2004, 108 (18), pp.5572-5581. ⟨10.1021/jp0375158⟩
- Accession number :
- edsair.doi.dedup.....090dee5ad117265e8019138351182610