Syntheses and Crystal Structures of a Series of Manganese-Lanthanide-Sodium 12-Metallacrown-4 Dimers
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ORIGINAL PAPER
Syntheses and Crystal Structures of a Series of Manganese‑Lanthanide‑Sodium 12‑Metallacrown‑4 Dimers Collin M. Foley1 · Maikel A. Armanious1 · Alyssa M. Smihosky1 · Matthias Zeller2 · Curtis M. Zaleski1 Received: 10 September 2020 / Accepted: 7 November 2020 © Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract A series of heterotrimetallic manganese-lanthanide-sodium dimer metallacrowns has been synthesized and characterized by single-crystal X-ray analysis: {LnNa[12-MCMn(III)N(shi)-4]}2(iph)4, where L nIII = 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; shi3− is salicylhydroximate; and iph2− is isophthalate. The manganese(III) ions and shi3− ligands generate the 12-MC-4 framework with one LnIII and Na+ ion bound to each [12-MCMn(III)N(shi)-4] on opposite sides of the central MC cavity. The carboxylate groups of the isophthalate ligands bridge between the central L nIII ion and each ring M nIII ion, and the meta-arrangement of the carboxylate groups joins two LnNa[12-MCMn(III)N(shi)-4] units together to form the dimer through the LnIII ions, which reside on the interior of the molecule. The identity of the central L nIII ion slightly impacts the size the [12-MCMn(III)N(shi)-4] III framework. As the crystal radius of the L n ion increases from L uIII (1.02 Å) to L aIII (1.19 Å), the 12-MC-4 framework III expands to accommodate the larger Ln ion as the MC cavity increases in size (0.53 Å for LuIII to 0.58 Å for LaIII) and the average cross cavity MnIII-MnIII and oxime oxygen-oxime oxygen distances also increase (MnIII-MnIII distances: 6.48 Å for LuIII to 6.52 Å for LaIII; Ooxime-Ooxime distances: 3.66 Å for LuIII to 3.75 Å for LaIII). In addition, the larger LnIII ions reside further from the MC cavity as indicated by the L nIII-oxime oxygen mean plane ( OoxMP) distance. The L nIII-OoxMP distance III III steadily decreases from La (1.7527(12) Å) to Lu (1.5575(15) Å).
* Curtis M. Zaleski [email protected] 1
Department of Chemistry and Biochemistry, Shippensburg University, Shippensburg, PA 17257, USA
Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA
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13
Vol.:(0123456789)
Journal of Chemical Crystallography
Graphic Abstract The complex {LaNa[12-MCMn(III)N(shi)-4]}2(iph)4(DMF)6(H2O)2 is a dimer of [12-MC-4] molecules linked by four isophthalate anions
Keywords Metallacrown · Manganese · Lanthanide · Heterotrimetallic
Introduction The typical metallacrown (MC) macrocyclic structure consists of a transition metal-nitrogen–oxygen ring repeat unit that generates a central cavity that is capable of binding a central metal ion, analogous to a crown ether [1]. Initially MCs were homometallic systems with the same metal ions in both the ring and central metal sites [2, 3]; however, heterobimetallic metallacrowns were quickly developed in the early 1990s [1, 4]. Yet it was not until 2014 that the firs
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