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 language | English |
|---|---|
| Pages (from-to) | 7778-7784 |
| Number of pages | 7 |
| Journal | Journal of the American Chemical Society |
| Volume | 111 |
| Issue number | 20 |
| Publication status | Published - 1989 Dec 1 |
| Externally published | Yes |
Fingerprint
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Highly cooperative valence detrapping of mixed-valence [Mn3O(O2CCH3)6(py)3](py) in the solid state. / Jang, Ho Gyeom; Vincent, John B.; Nakano, Motohiro; Huffman, John C.; Christou, George; Sorai, Michio; Wittebort, Richard J.; Hendrickson, David N.
In: Journal of the American Chemical Society, Vol. 111, No. 20, 01.12.1989, p. 7778-7784.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Highly cooperative valence detrapping of mixed-valence [Mn3O(O2CCH3)6(py)3](py) in the solid state
AU - Jang, Ho Gyeom
AU - Vincent, John B.
AU - Nakano, Motohiro
AU - Huffman, John C.
AU - Christou, George
AU - Sorai, Michio
AU - Wittebort, Richard J.
AU - Hendrickson, David N.
PY - 1989/12/1
Y1 - 1989/12/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=0000137651&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0000137651&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0000137651
VL - 111
SP - 7778
EP - 7784
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 20
ER -