Syntheses of High-spin Molecules

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Syntheses of High-spin Molecules H. Oshio Department of Chemistry, University of Tsukuba, Japan Workshop on the Quantum Dynamics of Molecular Magnets December 1 -4, 2002 Awaji Yumebutai International Conference Center

Single Molecule Magnets [Mn(III,IV)12O12(O2CR)16(H2O)] (S = 10) (T. Lis, 1980) [Mn(III,IV)12O12(O2CR)16(H2O)4]- (S = 19/2) [Mn(III,IV)4O3X(O2CMe)(dbm)3] (S = 9/2) [Fe(III)8O2(OH)12(tacn)6]8+ (S = 10) [V(III)4O2(O2CR)7(L-L)]+ (S = 3) D. N. Hendrickson, G. Christou, and D. Gatteschi

Single Molecule Magnet (SMM) Hext DE -Hext -Hext Magnetization Direction DE = |D|Sz2 DE :Energy barrier to reorientate between two possible directions of magnetizations D : Zero Field Splitting parameters SMM

Quantum Spin Tunneling Hext = 0 Tunneling Hext No Tunneling

Strategy for the High-spin Molecule Ferromagnetic Interactions by LMCT interactions AGK Theory P. W. Anderson (1959), J. B. Goodenough (1958), J. Kanamori (1959)

Cyanide Bridged Mixed Metal system [Fe2Cu2(m-CN) 4(bpy) 6] and [Fe2Cu2(m-CN) 4(bpy) 4(Rad) 2] [FeII2CuII2] [FeIII2CuII2] [FeIII2CuII2Rad2] dp dp dp ds ds ds ds ds dp ds dp dp S = 2 S = 3 S = 1/2x2 Inorg. Chem.

Strategy for the High-spin Molecule Ferromagnetic Interactions by LMCT interactions

High-spin Cluster Orthogonal arrangements of the magnetic orbitals

Bridging Ligands

Cu(II) cube of [Cu4(hsae)4]·2H2O J = 21 cm-1 Monoclinic C2/2 a = 25.355 (4) Å, b = 9.211(4) Å, c = 21.460(4) Å = 98.23(1)°, V = 4960(2) Å3, Z = 4 R = 0.04, Rw = 0.032 Angew. Chem. Int. Ed. Engl. 1977, 36, 2673.

Ni(II) Cube of [Ni4(sae)4(MeOH)4] Monoclinic P21/c a = 9.4504 (5) Å, b = 9.8801(5) Å, c = 15.4883(8) Å = 98.310(1)°, V = 1431.9(1) Å3, Z = 2 R1 = 0.0206, wR2 = 0.0553 Chem. Lett. 2002, 844.

Mn(II) Cube of [Mn4(sap)4(MeOH)4] g = 2.141 J = -1.6 cm-1 Tetragonal I41/a a = 16.8773 (6) Å, c =17.6920(16) Å V = 5039.4(5) Å3, Z = 4 R1 = 0.0339, wR2 = 0.1052 Chem. Lett. 2002, 1016.

Fe(II) Cube of [FeII4(sae)4(MeOH)4] triclinic P1- a = 13.3625(7) Å, b = 13.7572(7) Å, c = 14.2004(7) Å = 66.538(1)°, b = 74.973(1)°, g = 71.105(1), V = 2239.92(1) Å3, Z = 2 R1 = 0.0477, wR2 = 0.0959 J. Am. Chem. Soc. 2000. 122. 12603.

AC measurements of [FeII4(sae)4(MeOH)4]

Relaxation in [Fe4(sae)4(MeOH)4] with S =8 Ground State t = t0exp(DE/kT) t = 1/(2pnAC) nAC : Freq. of AC Field T : Temp. of max. in c” DE = |D|S2 = 64|D|

Summary Compounds in red are SMM. g C [emu mol-1 K]  [K] D [cm-1] E TB [Fe4(sap)4(MeO)4]·2H2O 2.261 15.43 9.56 +0.8 [Fe4(5-Br-sap)4(MeO)4] 2.227 14.86 9.32 +0.80 [Fe4(3-MeO-sap)4(MeO)4]·2MeOH 2.243 15.27 12.59 +1.15 [Fe4(sapd)4]·4MeOH·2H2O 2.180 14.29 4.57 +1.10 [Fe4(sae)4(MeO)4] 2.126 15.55 15.98 -0.76 28 1.1 [Fe4(5-Br-sae)4(MeO)4]·MeOH 2.209 14.57 15.68 -0.66 30 1.2 [Fe4(3,5-Cl2-sae)4(MeO)4] 2.120 13.44 13.99 -0.67 26 Compounds in red are SMM. The g, C, and  values were obtained from temperature dependence of the magnetic susceptibility. D values were estimated by the analyses of magnetization data at 1.8 K, supposing the only S = 8 being populated. E and TB values were estimated from the ac magnetic susceptibility measurements.

[FeII6FeIII(5-MeO-saeH)5 (5-MeO-sae)(m3-OMe)6] 7FeCl2·4H2O + 6(5-MeO-saeH2) + 1/21(t-Bu4N)(MnO4)  m2-phenoxo bridges S = 29/2 and D = +0.53 cm-1

Summary SMM of Ferrous Cubes Double Exchange System in a Fe(III)-Fe(II)-Fe(III) System Multinuclear Mixed Valent Fe(II,III) Systems Dinuclear Mn(III)-Cu(II) SMM