Chapter III Real-Time Tracing of the Melting Process of the Two Distinct Polymorphs of
III- 8. Torsional motions of other crystalline aromatic compounds
As mentioned in the introduction part of this chapter, large amplitude motions such as C–C torsional motion in biphenyl give a strong Raman intensity. The transoid 1,1′-binaphthyl in the present study can also be interpreted by the same reasoning. In the course of our study, we have found that some other molecules which have two polyaromatic rings connected by a σ-bond (either C–C or C–N single bond) show similar tendency. Their low-frequency Raman spectra are compared in figure III-19. Since these compounds are heavier than 1,1′-binaphthyl, the frequency of their torsional vibration (indicated in the figure) should be lower than the value for 1,1′-binaphthyl (26 cm−1). This is the case, as can be seen from figure III-19. In addition, transoid 1,1′-binaphthyl and these four compounds show similar spectral features in the range of 40–120 cm−1. These low-frequency Raman bands couple to each other and produce a high offset. From their crystal structures [77], we suppose that the coupling and high offsets might be due to π–π interactions between polyaromatic rings of neighboring molecules because the adjacent heavy rings stack in parallel to each other. These π–π interactions are intermolecular van der Waals-like attractive forces. The energy gap due to the π–π interactions is typically smaller than that of intramolecular vibrations (200–4000 cm−1).
Therefore, the Raman shift of such interactions appears in the low-frequency region (<200 cm−1). Furthermore, they split into a few peaks coupling to each other. We suspect that the Raman bands at 44, 55, 66, 79, and 95 cm−1 come from the same intermolecular interactions.
55
Figure III-19. Raman spectra of aromatic compounds containing the torsional motion.
9,9′-bianthryl
9-(9′-Anthryl) carbazole
9-(1′-naphthyl) carbazole
9,9′-bicarbazole
Transoid 1,1′-binaphthyl
56
Chapter IV
Conclusion
57
The constructed multichannel low-frequency Raman spectrometer with an I2-vapor containing cell as a Rayleigh rejection filter has been described. The iodine vapor filter has high Rayleigh scattering elimination efficiency, enabling us to measure Raman spectra down to ±5 cm−1 in both Stokes and anti-Stokes sides simultaneously. In addition, a wide spectral range (−200–+1100 cm−1) can be recorded without resort to scanning the grating of a spectrograph. Thanks to the high spectral reproducibility of the multichannel detection, the superfluous artifacts caused by the I2 vapor absorption are reduced to a negligible level just by using a simple and straightforward intensity correction method. Compared with existing metal vapor filters, the iodine vapor filter has a much narrower elimination bandwidth, free from complexity of adding fluorescence quenching gases.
We utilized the constructed Raman spectrometer to investigate the two crystal polymorphs of 1,1′-binaphthyl, a building block of the chiral catalyst. The Raman spectra of these two crystal forms showed distinct features in the low-frequency region (<200 cm−1), but no apparent difference was observed above 200 cm−1. Not only lattice vibrations but also intramolecular vibrations were observed in the low-frequency region. The most intense intramolecular vibrational band at 26 cm−1 of the transoid form was associated with the torsional motion around the interring C–C single bond, whereas the doublet peak around 100 cm−1 was assigned to be out-of-plane deformations. The torsional motion and out-of-plane vibration of 1,1′-binaphthyl were found to correlate with the interatomic distances between H(8)…H(8′), C(1)…H(2′), and C(1)…H(8′). With a better spectral resolution and polarized Raman measurements, it will be possible to assign each low-frequency Raman band of both forms of crystalline 1,1′-binaphthyl.
Real-time tracing of the melting process of the cisoid and transoid forms was done with rapid heating. A series of Raman spectra were recorded every 0.2 sec. Crystal structure loss manifested by spectral changes was seen in the low-frequency region. There remained the 26
58
cm−1 band of the transoid form and the 100 cm−1 band of the cisoid form even after melting.
This observation agrees with our prediction that these two bands arise from intramolecular vibrations rather than lattice vibrations. In addition, the sample temperature was determined by the Stokes/anti-Stokes intensity ratio. Seven symmetrized Lorentz functions convoluted with the Bose–Einstein factor were used to fit the low-frequency Raman spectra in both cisoid and transoid forms. Base on the high-quality fitted results, the sample temperature was determined to a high accuracy. The peak position of each low-frequency band was also determined and their change with temperature was discussed. Peak shifts due to thermal expansion in the transoid form were found to be smaller than those in the cisoid form. Thus, intermolecular interactions in the transoid form are supposed to be stronger than those in the cisoid form. It is consistent with the X-ray crystal structure reported in the literature.
As demonstrated in the present study, real-time tracing of solid samples with fast multichannel low-frequency Raman spectroscopy is a powerful and informative approach to phase transitions. A wealth of information on intermolecular interactions can be obtainable by using this technique. Bearing the advantages of low cost and short measurement time, our Raman apparatus provides deeper insights into the dynamical aspects of molecules compared with X-ray crystallography. If a faster read-out time detector is employed such as electron multiplying charge coupled device (EMCCD), it would be more helpful for understanding condensed phase dynamics.
59
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