Correlation between Metal鈥揑nsulator Transition and Hydrogen-Bonding Network in the Organic Metal 未-(BEDT-TTF)4[2,6-Anthracene-bis(sulfonate)]路(H2O)4

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• 作者：Franck Camerel ; Guillaume Le Helloco ; Thierry Guizouarn ; Olivier Jeannin ; Marc Fourmigu茅 ; Arkadiusz Fr膮ckowiak ; Iwona Olejniczak ; Roman 艢wietlik ; Andrea Marino ; Eric Collet ; Loic Toupet ; Pascale Auban-Senzier ; Enric Canadell
• 刊名：Crystal Growth & Design
• 出版年：2013
• 出版时间：November 6, 2013
• 年：2013
• 卷：13
• 期：11
• 页码：5135-5145
• 全文大小：664K
• 年卷期：v.13,no.11(November 6, 2013)
• ISSN：1528-7505

文摘

The sensitivity of electronic properties of organic conductors to minute modifications of their solid-state structure is investigated here within BEDT-TTF (ET) salts with organic bis-sulfonate anions, where specific hydrogen bonds between water molecules and sulfonate moieties are shown to dynamically control the organic slabs鈥?electronic structure. While the mixed-valence, 2,6-naphthalene-bis(sulfonate) salt, (ET)₄(NBS)路4H₂O, exhibits a charge order state already at room temperature, the corresponding salt with the 2,6-anthracene-bis(sulfonate) dianion, formulated as (ET)₄(ABS)路4H₂O, is metallic at RT and exhibits a metal鈥搃nsulator transition at T_MI = 85 K. The origin of the MI transition is revealed from a combination of temperature-dependent spectroscopic (Raman) measurements, X-ray structure elucidations (from 300 to 15 K), and theoretical investigations, demonstrating that the charge disproportionation observed below T_MI is associated here with the progressive switching of bifurcated OH路路路O hydrogen bonds between the sulfonate moieties of the anion and the trapped water molecules. These movements within the anion layer are transmitted through weaker C鈥揌路路路O interactions to the two A and B donor molecules, modifying the details of the overlap interactions within AA and BB pairs and opening a gap in the band structure.