Subtle Effects of Solvate Molecules on the Rate of Intramolecular Electron Transfer of Mixed-Valence Complexes in the Solid State

Ho G. Jang, Richard J. Wittebort, Michio Sorai, Yuki Kaneko, Motohiro Nakano, David N. Hendrickson

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Abstract

The microscopic nature of the valence-detrapping phase transition of [Fe3O(O2CCH3)6(4-Me-py)3](CHCl3) (2) is studied. The constant-pressure heat capacity of a 16.3703-g sample of 2 in the 14-300 K range is presented. An apparently first-order phase transition with two Cp peaks at 93.48 and 95.04 K was observed. After correction for the normal heat capacity, the total entropy gain for the phase transition was found to be ΔS = 17.18 ± 1.42 J K-1 mol-1, which is close to ΔS = R In 8 (=17.29 J K-1 mol-1). Isostructural [Fe3O(O2CCH3)6(py)3](CHCl3) (1) has been reported to have a “double-peaked” phase transition at ~208 K with ΔS = 28.10 ± 0.44 J K-1 mol-1, which is close to ΔS = R In 32 (=28.82 J K-1 mol-1). The valence-detrapping phase transition in both cases involves each Fe30 complex converting from being statically trapped in one vibronic state to dynamically interconverting between four vibronic states. For both 1 and 2, this contributes ΔS = R In 4. Even though it has been reported that the CHC13 solvate molecules in 1 cooperatively convert from being static in one lattice position to jumping between eight positions in the phase transition, the CHC13 molecules in 2 only start jumping between two positions where the C-H vector is pointing either up or down along the c axis (C3 axis). For 2, the CHC13 solvate molecules only contribute ΔS = R In 2. The nature of the motion of the chloroform solvate molecule is examined in detail by employing solid-state 2H NMR spectroscopy on magnetically oriented crystalline samples of [Fe30(02CCH3)6(4-Me-py)3](CDCl3). In these crystals, the C-D vector is jumping between positions on a cone axially symmetric about the C3 axis. At 290 K, this cone is ~ 18° off the C3 axis. A decrease in the temperature reduces this angle to 10° at 145 K and presumably 0° below the ~94 K phase transition. Thus, for complex 2 at the ~94 K phase transition the c axis of the crystal is too small to permit the chloroform C-H vector to precess about the c axis (C3 axis). The cooperative motion of the CHC13 molecules in 2 at ~94 K involve only a head-to-tail motion with the C-H vector on the c axis.

Original languageEnglish
Pages (from-to)2265-2271
Number of pages7
JournalInorganic Chemistry
Volume31
Issue number11
DOIs
Publication statusPublished - 1992

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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