Octanuclear heterometallic FeIII-CeIV pivalate clusters: From a close {Fe4Ce4(μ4-O)4} cage to an open {Fe4Ce4(μ4-O)2(μ3-O)2} core

Ultrasonic irradiation of trinuclear [Fe3O(O2CCMe3)(6)(H2O)(3)]Me(3)CCO(2)2(Me3CCO2H) or hexanuclear [Fe6O2 (OH)(2)(O2CCMe3)(12)] pivalate precursors with Ce(NO3)(6)6H(2)O, NaN3 and triethanolamine (H3tea) in MeOH/ MeCN solution results in the synthesis of two new octanuclear Fe-III-Ce-IV clusters formulated as [Fe4Ce4O4 (O2CCMe3)(4)(tea)(4)(N-3)(4)(MeOH)(4)].MeOH (1) and [Fe4Ce4O4(O2CCMe3)(6)(tea)(4)(N-3)(2)(MeOH)(2)]center dot 3(MeOH) (2). The spectroscopic and thermal properties of these compounds corroborate oxidation states and formula. Single crystal X-ray diffraction analysis revealed that the metal atoms in clusters 1 and 2 are organized in unprecedented close {Fe4Ce4(mu(4)-O)(4)} and open {Fe4Ce4(mu(4)-O)(2)(mu(3)-O)(2)} cores, respectively. The topology of these cores has not been observed before in FeIII-CeIV chemistry.

Automated summary

Ultrasonic irradiation leads to the synthesis of two new octanuclear Fe-III-Ce-IV clusters with unique metal core structures.