Highly cooperative valence detrapping of mixed-valence [Mn3O(O2CCH3)6(py)3](py) in the solid state

Ho Gyeom Jang, John B. Vincent, Motohiro Nakano, John C. Huffman, George Christou, Michio Sorai, Richard J. Wittebort, David N. Hendrickson

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Abstract

Heat capacity at constant pressure versus temperature data for [Mn3O(O2CCH3)6(py)3](py) show that there is a first-order phase transition at 184.65 K. The phase transition is characterized by total enthalpy and entropy gains of ΔH = 6460 J mol-1 and ΔS = 35.77 J K-1 mol-1, respectively. The experimental ΔS is approximately equal to R ln 72 and is accounted for by two contributions: the Mn3O complexes converting from valence trapped to valence detrapped (R ln 4) and the pyridine solvate molecules converting from being static to dynamically gaining access to 18 different orientations (R ln 18). The 18 different solvate molecule orientations result from the plane of each pyridine solvate jumping between three positions about the C3 crystal axis, together with a rotation in each position about a local pseudo C6 axis. To account for the 2H NMR results the average orientation of the plane of the pyridine is not along the C3 axis, but tipped off of it by ∼15°. Variable-temperature 2H NMR for a single crystal of [Mn3O(O2CCD3)6(py)3](py) oriented with the magnetic field parallel to the c axis establishes that there is an abrupt valence detrapping at the phase transition. Detailed 2H NMR experimentation employing a new selective irradiation technique on a single crystal of [Mn3O(O2CCH3)6(C5D 5N)3](C5D5N) verifies the onset and mechanism of motion of the pyridine solvate molecule at the phase transition. An explanation is given as to why the present Mn3O complex exhibits valence detrapping abruptly in a first-order phase transition, whereas the isostructural Fe3O complex valence detraps gradually in a higher order phase transition.

Original languageEnglish
Pages (from-to)7778-7784
Number of pages7
JournalJournal of the American Chemical Society
Volume111
Issue number20
Publication statusPublished - 1989 Dec 1
Externally publishedYes

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ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Jang, H. G., Vincent, J. B., Nakano, M., Huffman, J. C., Christou, G., Sorai, M., Wittebort, R. J., & Hendrickson, D. N. (1989). Highly cooperative valence detrapping of mixed-valence [Mn3O(O2CCH3)6(py)3](py) in the solid state. Journal of the American Chemical Society, 111(20), 7778-7784.