Syntheses and Crystal Structures of a Series of Manganese-Lanthanide-Sodium 12-Metallacrown-4 Dimers

• Published in: Journal of chemical crystallography Vol. 51; no. 4; pp. 465 - 482
• Main Authors: Foley, Collin M., Armanious, Maikel A., Smihosky, Alyssa M., Zeller, Matthias, Zaleski, Curtis M.
• Format: Journal Article
• Language: English
• Published: New York Springer US 01.12.2021; Springer Nature B.V
• Subjects: Chemistry; Chemistry and Materials Science; Crystal structure; Crystallography and Scattering Methods; Crystals; Dimers; Erbium; Gadolinium; Inorganic Chemistry; Ligands; Manganese; Organometallic Chemistry; Original Paper; Oxygen; Physical Chemistry; Single crystals; Sodium; X ray analysis; Ytterbium; Yttrium; Heterotrimetallic; Lanthanide; Metallacrown; Manganese
• ISSN: 1074-1542; 1572-8854
• DOI: 10.1007/s10870-020-00870-1

A series of heterotrimetallic manganese-lanthanide-sodium dimer metallacrowns has been synthesized and characterized by single-crystal X-ray analysis: {LnNa[12-MC Mn(III)N(shi) -4]} 2 (iph) 4 , where Ln III  = La ( 1) , Ce ( 2 ), Pr ( 3 ), Nd ( 4 ), Sm ( 5 ), Eu ( 6 ), Gd ( 7 ), Tb ( 8 ), Dy ( 9 ), Ho ( 10 ), Er ( 11 ), Tm ( 12 ), Yb ( 13 ), Lu ( 14 ), and Y ( 15 ); MC is metallacrown; shi 3− is salicylhydroximate; and iph 2− is isophthalate. The manganese(III) ions and shi 3− ligands generate the 12-MC-4 framework with one Ln III and Na + ion bound to each [12-MC Mn(III)N(shi) -4] on opposite sides of the central MC cavity. The carboxylate groups of the isophthalate ligands bridge between the central Ln III ion and each ring Mn III ion, and the meta -arrangement of the carboxylate groups joins two LnNa[12-MC Mn(III)N(shi) -4] units together to form the dimer through the Ln III ions, which reside on the interior of the molecule. The identity of the central Ln III ion slightly impacts the size the [12-MC Mn(III)N(shi) -4] framework. As the crystal radius of the Ln III ion increases from Lu III (1.02 Å) to La III (1.19 Å), the 12-MC-4 framework expands to accommodate the larger Ln III ion as the MC cavity increases in size (0.53 Å for Lu III to 0.58 Å for La III ) and the average cross cavity Mn III -Mn III and oxime oxygen-oxime oxygen distances also increase (Mn III -Mn III distances: 6.48 Å for Lu III to 6.52 Å for La III ; O oxime -O oxime distances: 3.66 Å for Lu III to 3.75 Å for La III ). In addition, the larger Ln III ions reside further from the MC cavity as indicated by the Ln III -oxime oxygen mean plane (O ox MP) distance. The Ln III -O ox MP distance steadily decreases from La III (1.7527(12) Å) to Lu III (1.5575(15) Å). Graphic Abstract The complex {LaNa[12-MC Mn(III)N(shi) -4]} 2 (iph) 4 (DMF) 6 (H 2 O) 2 is a dimer of [12-MC-4] molecules linked by four isophthalate anions