Two new clusters with MnII-MnIV magnetic exchange from the use of polyalcohol ligands. Issue 5 (4th March 2017)

• Record Type: Journal Article
• Authors: Huo, De-Biao; Leng, Ji-Dong; Wang, Jing; Wang, Zi-Zhou; Lu, Wan-Ming; Hong, Xiao-Shuo; Zhou, Ai-Ju; Lin, Yan-Yong
• Is Part Of: Journal of coordination chemistry. Volume 70:Issue 5(2017)
• Page Start: 936
• Page End: 948
• Publication Date: 2017-03-04
• Subjects: Disk-like heptanuclear -- polyalcohol ligands -- mixed-valence manganese -- defective dicubane core -- ferromagnetic interactions; Coordination compounds -- Periodicals; 541.2242
• DOI: 10.1080/00958972.2017.1284321
• Languages: English
• ISSNs: 0095-8972

Abstract

Abstract: Two mixed-valence Mn(II, IV) complexes, [Mn II 4 Mn IV 3 (teaH)3 (tea)(thmeH)3 (thme)](ClO4 )2 ·3MeCN (1 ) and [Mn II 2 Mn IV 2 (edteH)2 (peolH)2 ]·4MeOH (2 ), where H4 edte = N, N, N′, N′-tetrakis(2-hydroxyethyl)ethylenediamine, teaH3 = tris(2-hydroxyethyl)amine, H4 peol = pentaerythritol, and H3 thme = 1, 1, 1-tris(hydroxymethyl)ethane, were prepared from the corresponding manganese salts and mixed ligands with polyalcohols. The two clusters consist of a trapped-valence polynuclear core comprising 4Mn II and 3Mn IV for1, 2Mn II and 2Mn IV ions for2 . Complex1 crystallizes in the rhombohedral space group R 3c, while2 crystallizes in the monoclinic space group P 21 /c. Complex1 consists of a near-planar Mn7 unit that comprises a Mn6 hexagon of alternating Mn II and Mn IV ions surrounding a central Mn II ion. The remaining coordinated sites are occupied by eight different deprotonation degrees of H3 tea or H3 thme. The tetranuclear cluster of2 consists of a fused defective dicubane Mn4 O6 core, and the four Mn ions are coordinated by oxygens from edteH 3− and peolH 3− into an unusual butterfly-like [Mn II 2 Mn IV 2 ] topology. The two clusters are also characterized by mass spectra and X-ray photoelectron spectroscopy. Direct current magnetization studies reveal ferromagnetic interactions within both Mn clusters. Abstract :