Facile carboxylate ligand variation of heterotrimetallic 12-metallacrown-4 complexes. (16th August 2016)

• Record Type: Journal Article
• Authors: Travis, Jordan R.; Zeller, Matthias; Zaleski, Curtis M.
• Is Part Of: Polyhedron. Volume 114(2016)
• Page Start: 29
• Page End: 36
• Publication Date: 2016-08-16
• Subjects: Metallacrown -- Heterotrimetallic -- Coordination complex -- Self-assembly -- Supramolecular; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2015.09.006
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: Three single-crystal X-ray structures of a series of Er III Na ( L ) 4 [ 12 - MC Mn III ( N ) shi - 4 ] complexes, where L is either trimethylacetate, benzoate, or salicylate and shi 3− is salicylhydroximate, are presented. The self-assembled supramolecular coordination complexes demonstrate the ability to vary the bridging carboxylate monoanion in this heterotrimetallic family of compounds. Abstract: Single crystal X-ray structures are presented for three 12-metallacrown-4 complexes, Er III Na ( L ) 4 [ 11 - MC Mn III ( N ) shi - 4 ], where L is trimethylacetate (OTMA), benzoate (OBen), or salicylate (OSal), MC is metallacrown, and shi 3− is salicylhydroximate: Er III Na(OTMA)4 [ 12 - MC Mn III ( N ) shi - 4 ](H2 O)3.73 (DMF)0.27 ·7.45DMF·1.47H2 O, 1, Er III Na(OBen)4 [ 12 - MC Mn III ( N ) shi - 3 ](H2 O)4 ·4DMF·0.87H2 O, 2, and Er III Na(OSal)4 [ 12 - MC Mn III ( N ) shi - 4 ](H2 O)3.54 (DMF)0.73 ·4DMF·0.24H2 O, 3, where DMF is N, N -dimethylformamide. Compounds1 –3 demonstrate the facile ligand variation of a self-assembled supramolecular coordination complex containing three different metal types. In all three structures, the monoanion carboxylate ligands serve as bridges between the central Er III ion and the ring Mn III ions. The structures of1 –3 are all domed towards the side of the central Na + ion, and the 12-MC-4 frameworks of1 –3 are very similar regardless of the monoanion carboxylate bridge, as the metallacrown cavity radii of1 –3 are 0.55 Å, 0.54 Å, and 0.55 Å, respectively. In addition, the cross cavity measurements indicate that the metallacrown frameworks are not significantly altered by the presence of different monoanion carboxylate ligands as the Mn III –Mn III cross cavity distances for1 –3 are 6.52 Å, 6.51 Å, and 6.49 Å, respectively, and the oxime oxygen–oxime oxygen cross cavity distances for1 –3 are 3.71 Å, 3.68 Å, and 3.69 Å, respectively. The conservation of the 12-MC-4 framework among the different structures will be important when assessing the physical and chemical properties of this class of molecules.