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Proton Relay in a One-Dimensional Hydrogen-Bonded Chain Composed of Water Molecules and a Squaric Acid Derivative

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journal contribution
posted on 05.10.2001 by Hiroshi Terao, Tadashi Sugawara, Yasuo Kita, Naoki Sato, Eriko Kaho, Sadamu Takeda
The crystal structure of a hydrated crystal of bis(squaryl)biphenyl (BSQB·4H2O), in which two squaric acid moieties are connected with a 4,4‘-biphenyl unit, was characterized by the presence of a one-dimensional hydrogen-bonded chain composed of BSQB and water molecules. X-ray crystallographic analysis showed that BSQB exists in a dianion form and that, on average, two of the four water molecules are protonated. The enhanced temperature dependence of the thermal parameters of the oxygen atoms of the water molecules suggested dynamic disorder of the water molecules. The solid-state magic angle spinning deuterium NMR spectrum of BSQB·4D2O revealed that deuterons are exchanged between heavy water molecules and oxonium ions with an exchange rate of ca. 700 Hz around 250 K and that deuterons start to migrate in a hydrogen-bonded cluster of water molecules. Ac dielectric measurements were also used to examine the dynamic process in the hydrated crystal. The dielectric permittivity of the crystal dramatically increased above 250 K with a distinct frequency dependence (ε‘ = 4.7 × 104 at 340 K and 1 kHz). The frequency dependence of tan δ at 290 K exhibited a maximum at 3.0 kHz, and this maximum shifted to lower frequencies when the temperature of the crystal decreased. These experimental results suggested that in the one-dimensional hydrogen-bonded chain of BSQB·4H2O a proton relay between oxonium ions and water molecules occurred within a cluster of four water molecules and that the relay was transmitted to the adjacent cluster mediated by the modulation of the negative charge distribution of the BSQB dianion. These phenomena were interpreted as the solitonic migration of the charged domain boundaries along the one-dimensional hydrogen-bonded chain.