title: Vibrational and theoretical study of diacetylenic acids.
abstract: Three selected diacetylenic acids (DAs) with side-chains of various length (CH3-(CH2)m-C≡C-C≡C(CH2)n-COOH, where m=7, 9, 11, and n=3, 8) were analyzed using vibrational spectroscopy and quantum-chemical calculations. The conformational analysis was followed by potential energy distribution (PED) calculations to gain deeper insight into their FT-Raman and FT-IR spectra. The analysis was focused on spectral features of the diacetylene system sensitive to the substitution. In particular, the electron donor-acceptor properties of the substituent and the influence of side-chain length were studied. FT-IR spectra were measured by using two techniques, i.e. transmission (with KBr substrate) and Attenuated Total Reflection (ATR), and the latter seems to be less adequate for DAs measurements because the bands in the fingerprint region as well as the ν(C≡C)as mode are relatively of low intensity. Additionally, polymerization process of DAs was recognized using FT-Raman spectroscopy and strong and well-separated bands of diacetylenic polymers. Temperature and exposure to the sunlight are the factors of an important influence on the polymerization process of DAs. Since the investigated DAs are carboxylic acids, the interpretation of experimental spectra was performed on the basis of monomer and dimer calculations.
authors.affiliation: Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland.
authors.forename: Maciej
authors.initials: M
authors.lastname: Roman
authors.affiliation: Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland; Jagiellonian Center for Experimental Therapeutics (JCET), Jagiellonian University, Bobrzynskiego 14, 30-348 Krakow, Poland. Electronic address: baranska@chemia.uj.edu.pl.
authors.forename: Malgorzata
authors.initials: M
authors.lastname: Baranska
mesh_terms: D000114:Acetylene / Q000737:chemistry*; D000143:Acids / Q000737:chemistry*; D001965:Bromides / Q000737:chemistry; D019281:Dimerization; D006863:Hydrogen-Ion Concentration; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D017680:Potassium Compounds / Q000737:chemistry; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet; D017550:Spectroscopy, Fourier Transform Infrared; D014732:Vibration
chemical_list: D000143:Acids; D001965:Bromides; D017680:Potassium Compounds; D000114:Acetylene; C039004:potassium bromide
keywords: ATR; DFT; Diacetylenic acids; Infrared; Polymerization; Raman