Ionic Conductivities Induced by the Partial Solvent Molecule Removal from Diruthenium(II,III) Adamantanecarboxylate Salts

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  • Norihisa Hoshino
    Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan
  • Tomoyuki Akutagawa
    Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan

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説明

Ionic conductivities are observed in the BF 4 – salts of the Ru 2 (II,III) dinuclear paddlewheels with adamantyl carboxylates [Ru II,III 2 (R-AdCOO) 4 (MeOH) 2 ]­BF 4 ·MeOH (R-AdCOO – = 3-R-adamantanecarboxylate, 1 , R = H; 2 , R = F; and 3 , R = OH), according to the partial removal of the solvent MeOH molecules. In the crystal structures of 1 – 3 , disordered MeOH molecules and BF 4 – ions are found at the neighboring sites surrounded by the adamantyl groups. The packing structures of 1 and 2 are almost identical, whereas 3 crystallizes in a different structure from that of 1 and 2 , accompanied by a hydrogen-bonding network between the 3-OH-adamantyl groups. In the electron density maps at 300 K, the globular adamantyl groups of 1 and 2 fluctuate severely, whereas no significant fluctuations of the 3-OH-adamantyl group are found in 3 . The impedance data are collected for the freshly prepared crystals of 1 – 3 during heating, and the data are analyzed using an equivalent circuit containing a frequency-independent capacitance ( ε r 1 ), a capacitance following a Debye-type relaxation ( ε r 2 ), and a conductive component ( σ 4 ) in the range of 78–350 K. At approximately 200 K, the ε r 2 values increase and semicircles are observed in the complex permittivity plots, corresponding to the orientational polarization of the MeOH molecules enclosed in the disordered sites surrounded by the adamantyl groups. The ε r 2 values of 1 and 2 are much larger than those of 3 because of the fluctuations in the adamantyl units surrounding the MeOH solvent molecule. At approximately 300 K, the σ 4 values are highly evolved and semicircles are found in the complex impedance plots. Gradual weight losses are observed in the thermogravimetries at approximately 300 K, and the ionic conductivities are probably induced by the partial removal of the MeOH molecules neighboring the BF 4 – ions. The σ 4 values of 3 are much larger than those of 1 and 2 , which could be attributed to the robust framework of the hydrogen bonds between the ...

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