Structural insights into anhydrous and monohydrated forms of 2,4,6-trihydroxybenzoic acid based on Raman and terahertz spectroscopic characterization

Abstract In order to characterize molecular structures of 2,4,6-trihydroxybenzoic acid (PCA) by means of vibrational spectroscopic techniques, we report investigation of PCA monohydrated form and its anhydrous polymorphic one by using terahertz and Raman spectral characterization. The experimental THz spectra show that the monohydrated PCA only has two absorption bands at 0.69 and 1.65 THz respectively in the frequency region from 0.2 to 1.8 THz, meanwhile the anhydrous form has a few significantly different absorption bands at 0.75, 1.01, 1.46 and 1.64 THz, respectively. Furthermore, Raman spectra characterized such differences of vibrational modes shown within 200–1800 cm−1 region about the monohydrated and anhydrous forms of PCA. In view of various possible theoretical structural forms that may exist in anhydrous PCA and its monohydrated one, density functional theory calculations were performed to simulate optimized structures and vibrational mode of above two PCA polymorphic forms. Theoretical results and experimental THz/Raman spectra of anhydrous PCA show that the dimer synthon via the carboxylic group ••• carboxyl group and its ortho-phenolic hydroxyl group inter-molecular hydrogen bonding interaction establishing the theoretical form I (AH-I) is more consistent with experimental observations than other theoretical forms (AH-II and AH-III). Meanwhile, the theoretical monohydrated form I (MH-I), which is formed by the linkage of carboxyl group and its ortho-phenolic hydroxyl group with water molecule, is also much more agreement with experimental spectral observations of PCA monohydrate than other monohydrated forms (MH-II and MH-III). Our study demonstrate effectively qualitative analysis of both micro-molecular structures and dehydrated transitions between anhydrous and hydrated polymorphic forms of PCA, thus providing rich information on the corresponding structural changes of anhydrous and hydrated PCAs due to various inter-molecular and intra-molecular interactions based on their finger-print vibrational spectra combined with theoretical simulations.