Aqueous chemistry of high-valent manganese. Structure, magnetic, and redox properties of a new type of Mn-Oxo cluster, [Mn[sup IV] [sub 4]O[sub 6](bpy)[sub 6]][sup 4+]. Relevance to the oxygen evolving center in plants

Journal Article · Wed Sep 21 00:00:00 EDT 1994 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00098a016· OSTI ID:6845507

Philouze, C; Blondin, G; Girerd, J J ^[1]; Guilhem, J; Pascard, C ^[2]; Lexa, D ^[3]

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1. Universite Paris-Sud (France)
2. Institut de Chimie des Substances Naturelles, Gif-sur-Yvette (France)
3. Universite Paris VII (France)

The tetranuclear species [Mn[sup IV] [sub 4]O[sub 6] (bpy)[sub 6]] (ClO[sub 4])[sub 4][center dot]H[sub 2]O was isolated from an aqueous nitric acid solution (pH = 2) of Mn[sup III] (bpy) Cl[sub 3](H[sub 2]O) upon addition of NaClO[sub 4]. It crystallizes in the triclinic space group P[bar l] with a = 20.213(7) [angstrom], b = 13.533(7) [angstrom], c = 13.411(8) [angstrom], [alpha] = 112.01(8)[degree], [beta] = 96.72(11)[degree], [gamma] = 100.34(12)[degree], V = 3276.9 [angstrom][sup 3], and Z = 2. The cation has a nonrectilinear chain structure [(bpy)[sub 2]Mn[sup IV[sub a]]O[sub 2]Mn[sup IV[sub b]](bpy)O[sub 2]Mn[sup IV[sub c]](bpy)O[sub 2]Mn[sup IV[sub d]](bpy)[sub 2]][sup 4+]. The metal-metal distances are Mn[sub a]-Mn[sub b] = 2.746(5) [angstrom], Mn[sub b]-Mn[sub c] = 2.760(5) [angstrom], Mn[sub c]-Mn[sub d] = 2.735(4) [angstrom], Mn[sub a]-Mn[sub c] = 4.899(10) [angstrom], Mn[sub b]-Mn[sub d] = 4.897(6) [angstrom], and Mn[sub a]-Mn[sub d] = 6.419(11) [angstrom]. The variable temperature magnetic susceptibility data for [Mn[sup IV[sub 4]]O[sub 6](bpy)[sub 6]](ClO[sub 4])[sub 4][center dot]H[sub 2]O in the range 12-294 K were fit using the spin Hamiltonian H[sub S] = J[sub ab]S[sub a]S[sub b] -J[sub bc]S[sub b]S[sub c] - J[sub cd]S[sub c]S[sub d], with J[sub ab] = J[sub cd] = -176 cm[sup [minus]1] and J[sub bc] = [minus]268 cm[sup [minus]1]. 55 refs., 11 figs., 3 tabs.

• OSTI ID: 6845507
• Journal Information: Journal of the American Chemical Society; (United States), Vol. 116:19; ISSN 0002-7863
• Country of Publication: United States
• Language: English

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MAGNETIC SUSCEPTIBILITY
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