Systematic Expansion of Supercubane Cores in Manganese Oxo Clusters with Tricarboxylate Ligands

作者：Okui Yayoi; Catusanu Florina Aurelia; Kubota Ryoko; Kure Bunsho; Nakajima Takayuki; Tanase Tomoaki^*; Kajiwara Takashi; Mikuriya Masahiro; Miyasaka Hitoshi; Yamashita Masahiro

来源：European Journal of Inorganic Chemistry, 2011, 2011(28): 4325-4330.

DOI：10.1002/ejic.201100781

• Manganese
• Carboxylate ligands
• Mixed-valent compounds
• Cluster compounds
• Supercubane cores
• Magnetic properties

A novel class of high-nuclearity Mn-17 and Mn-19 mixed-valent complexes, [Mn-17(mu-O)(12)(mu-OMe)(2)(mu-kta)(6)(MeOH)(4)] (1), [Mn-17(mu-O)(14)(mu-kta)(6)L-4] [L = bpy (2a), phen (2b), 4,7-Ph(2)phen (2c), dmf (3)], and [Mn-19(mu-O)(14)(mu-kta)(6)(bpy)(6)]X-3 [X = PF6 (4a), BF4 (4b)], were synthesized by utilizing Kemp's tricarboxylate ligands (H(3)kta = cis,cis-1,3,5-trimethylcyclohexane-1,3,5- tricarboxylic acid). The complexes were characterized by X-ray crystallography and reveal mineralomimetic Mn-13 supercubane units, [Mn-13(mu-O)(14)], in which their oxidation states systematically altered, depending on their vertex face-capping ligands and Mn-II satellite fragments. Complex 2a was converted by treatment with benzoic acid and [Mn2O2(bpy)(4)](BF4)(3) to a cage-type Mn-14 complex, [Mn-14(mu-O)(12)(mu-OH)(6)(mu-Hkta)(6)(bpy)(6)](BF4)(4) (5), which show ferro- and antiferromagnetic interactions and slow magnetic relaxation at low temperature.

• 出版日期2011-10