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| Since the beginning of the 1990s, high-spin complexes exhibiting ¡°Single-Molecule Magnets¡± (SMMs) behavior have received a wide attention not only for their interests in fundamental physics, but also for their potential application in information storage or devices for future quantum computers[1-3]. Hhmp is widely applied in the research of this field, at present, the Mn clusters which are synthesized by the ligand play an important role in the filed of SMMs, for example, [Mn10O4(N3)4(hmp)12]X2(X=N3-,ClO4-)[5], it is difficult to predict what type of topolopy and structure will lead to a hing-spin cluster and even more difficult to then synthesize such a species, Moreever, it is also important in this area of chemistry to not only make new examples of high-spin molecules and SMMs, but also to build up families of related compounds so that structure-property relations can be investigated.[Mn25O18(OH)(OMe)(hmp)6(pdm)6 (pd mH)6]•(ClO4)6•(MeCN)4[6], [Mn18(O)14(O2CMe)18(hmp)4(hmpH)2(H2O)2]•6CH2Cl2[7], [Mn21O14 (OH)2(O2CMe)16(hmp)8(pic)2(py)(H2O)](ClO4)4[8], [M18O14(O2CR)18(hmp)4(hmpH)2(H2O)2] (R= Me,Et)[9], [Mn7(OH)3 (hmp)9 Cl3](Cl)(ClO4)[10], these complexes have been shown to function as SMMs. The ligand not only play an important role in the Mn/hmp complexes, but also in the other metal-complexes. Those complexes also show the SMMs behavior, such as [Co4(hmp)4(MeOH)4Cl4][11], [Ni(hmp) (ROH)Cl]4 (R=CH3; CH2CH3; CH2CH3C(CH3)3)[12]. Since 2001, the first MnII2MnIII2 mixed-valence tetranuclear SMMs [Mn4(hmp)6Br2(H2O)2]Br2•4H2O was reported[13a,b], many complexes [14a,14b,14c,14d,14e,14f] possesses a similar double-cubical [Mn4] core with various terminal ligands that are always either coordinating anions or solvent molecules on its MnII sites, and most of those complexes exhibit SMMs behavior. From this point of view and as illustrated by the present work, the Mn4/hmp SMM complexes form a new family of complexes that fulfill the above appealing assets of the SMMs. |
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