Quantum tunneling and quantum phase interference in a [MnII2MnIII2] single-molecule magnet

[Mn-4(hMP)(6)(H2O)(2)(NO3)(2)](NO3)(2)center dot 2.5H(2)O (1) has been synthesized from the reaction of 2-hydroxymethylpyridine (Hhmp) with Mn(NO3)(2)center dot 4H2O in the presence of tetraethylammonium hydroxide. 1 crystallizes in the triclinic P (1) over bar space group with two crystallographically independent centrosymmetrical [Mn-4(hmp)(6)(H2O)(2)(NO3)(2)](2+) complexes in the packing structure. Four Mn ions are arranged in a double-cuboidal fashion where outer Mn2+ are heptacoordinated and inner Mn3+ are hexacoordinated. dc magnetic measurements show that both Mn2+center dot center dot center dot Mn3+ and Mn3+center dot center dot center dot Mn3+ interactions are ferromagnetic with J(wb)/k(B) = +0.80(5) K, and J(bb)/k(B) = +7.1(1) K, respectively, leading to an S-T = 9 ground state. Combined ac and dc measurements reveal the single-molecule magnet (SMM) behavior of 1 with both thermally activated and ground-state tunneling regimes, including quantum phase interference. In the thermally activated regime, the characteristic relaxation time (tau) of the system follows an Arrhenius law with tau(0) = 6.7 x 10(-9) s and Delta(eff)/k(B) = 20.9 K. Below 0.34 K, tau saturates indicating that the quantum tunneling of the magnetization becomes the dominant relaxation process as expected for SMMs. Down to 0.04 K, field dependence of the magnetization measured using the mu-SQUID technique shows the presence of very weak inter-SMM interactions (zJ'/k(B) approximate to -1.5 x 10(-3) K) and allows an estimation of D/k(B) at -0.35 K. Quantum phase interference has been used to confirm the D value and to estimate the transverse anisotropic parameter to E/k(B) = +0.083 K and the ground-state tunnel splitting Delta(LZ) = 3 x 10(-7) K at H-trans = 0 Oe. These results rationalize the observed tunneling time (tau(QTM)) and the effective energy barrier (Delta(eff)).