Two-Dimensional Infrared Spectroscopy and Principal Component Analysis Studies on a New Azobenzene Derivative Supramolecular System Based on Hydrogen Bonds

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Infrared (IR) spectra of a supramolecular assembly with an azobenzene derivative and intermolecular hydrogen bonds have been measured in the temperature range from 30 to 200 °C to investigate heat-induced structural changes and thermal stability. Principal component analysis (PCA) and two kinds of two-dimensional (2D) correlation spectroscopy, variable–variable (VV) 2D and sample–sample (SS) 2D spectroscopy, have been employed to analyze the observed temperature-dependent spectral variations. The PCA and SS 2D correlation analyses have demonstrated that the complete decoupling of hydrogen bonds in the supramolecular assembly occurs between 110 and 115 °C, which is in good agreement with the results of a differential scanning calorimetry (DSC) study for the heating process. The PCA of the IR spectra in the region of 3600–3100 cm-1 has illustrated that there are at least four principal components for the different NH2 and CONH species in the present supramolecular system. The VV 2D correlation spectroscopy study has provided information about the structure and strength of hydrogen bonds of NH2 and CONH groups and their temperaturedependent variations. The different species of hydrogen-bonded NH2 and CONH groups in the supramolecular system can be clarified by the VV 2D correlation analysis. The VV 2D correlation analysis has also revealed the specific order of the temperatureinduced changes in the hydrogen bonds of NH2 and CONH groups.
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