17O NQR and 13C NMR study of hydrogen-bonded organic ferroelectric croconic acid

• Published in: Physica Status Solidi (b) Vol. 248; no. 9; pp. 2091 - 2096
• Main Authors: Seliger, Janez, Plavec, Janez, Šket, Primož, Žagar, Veselko, Blinc, Robert
• Format: Journal Article
• Language: English
• Published: Berlin WILEY-VCH Verlag 01.09.2011; WILEY‐VCH Verlag
• Subjects: Correlation; croconic acid; double resonances; Ferroelectric materials; Ferroelectricity; Hydrogen bonds; NMR; Nuclear magnetic resonance; nuclear quadrupole resonances; organic ferroelectrics; Quadrupole interaction; Quadrupoles; Spectra
• ISSN: 0370-1972; 1521-3951; 1521-3951
• DOI: 10.1002/pssb.201046649

The 1H17O nuclear quadrupole double resonance spectrum and the 13C CP/MAS NMR spectrum of polycrystalline croconic acid, H2C5O5, have been studied at room temperature. Croconic acid has been recently shown to have the highest switchable spontaneous polarization of all organic ferroelectrics and stays polarized up to the decomposition point at around 450 K. Both the 13C NMR and the 17O nuclear quadrupole resonance (NQR) spectra show that there are five crystallorgaphically non‐equivalent carbon and oxygen positions for a given molecule and that therefore the two OH…O bonds are non‐equivalent. From the dipolar structure of the 17O quadrupole resonance spectra the OH distance is determined as being 0.099 ± 0.001 nm in both hydrogen bonds. The large 17O quadrupole coupling constant at the COH as well as at the CO…H oxygen position and the short OH distance demonstrate that the OH…O hydrogen bonds are strongly asymmetric. A correlation of the 17OH…O and OH…17O quadrupole coupling constants versus the O…O distance has been observed in several organic acids. The data for croconic acid significantly deviate from this correlation, what may be the result of the strong long range ferroelectric ordering which influences the electron distribution in the hydrogen bonds.