Syntheses and Crystal Structures of a Series of Dysprosium–Manganese–Sodium 12-Metallacrown-4 Compounds with Halogenated Benzoate Bridging Anions

Crystal structure of a heterotrimetallic 12-metallacrown-4 with 2-propylvalerate anion bridges

“…Therefore, 2-hydroxybenzoate is the most electron-withdrawing in the series, and this may affect the magnetic coupling between the Dy III and Mn III ions. We have also extended the types of DyNaY 4 [12-MC Mn III Nshi -4] structures by synthesizing complexes with 3-hydroxy-and 4-hydroxybenzoate (Manickas et al, 2020) and with halogenated benzoate anions (2-fluoro-, 3-fluoro-, 4-fluoro-, 2-chloro-, 3-chloro-, 3-bromo-, and 2-iodobenzoate; (Michael et al, 2021). These carboxylates have a range of pK a values that spans from 2.86 to 4.57 (Haynes, 2010), although at this time we have not investigated the SMM properties of these compounds.…”

“…A range of bridging carboxylate anions (Y) have been used including acetate (OAc), trimethylacetate (TMA), benzoate (ben), 2-hydroxybenzoate (2-OHben), 3-hydroxybenzoate (3- OHben), 4-hydroxylbenzoate (4-OHben), 2-fluorobenzoate (2-Fben), 3-fluorobenzoate (3-Fben), 4-fluorobenzoate (4-Fben), 2-chlorobenzoate (2-Clben), 4-chlorobenzoate (4-Clben), 3-bromobenzoate (3-Brben), and 2-iodobenzoate (2-Iben). Of the forty structures, thirteen contain both Dy III and Na + as in 1 (Azar et al, 2014;Boron et al, 2016;Manickas et al, 2020;Michael et al, 2021). The structural comparison of 1 will be limited to the MCs that contain Dy III and Na + ions captured in the central MC cavity (Table 5).…”

“…A survey of the Cambridge Structural Database (CSD version 5.43, update September 2022, Groom et al, 2016) reveals forty LnXY 4 [12-MC Mn III N(shi) -4] structures, where X is a countercation with a 1+ charge and Y is a carboxylate anion (Azar et al, 2014;Travis et al, 2015Travis et al, , 2016Boron et al, 2016;Cao et al, 2016;Qin et al, 2017;Anthanasopoulou et al, 2018;Manickas et al, 2020;Michael et al, 2021). The central Ln III metal ions include the lanthanide ions from Pr to Yb (except Pm) and yttrium.…”

Visible and near-infrared emitting heterotrimetallic lanthanide–aluminum–sodium 12-metallacrown-4 compounds: discrete monomers and dimers

“…In a series of manganese–lanthanide 12-MC-4 complexes LnNaX 4 [12-MC Mn(III)N(shi) -4], where X is a carboxylate anion and shi 3− is salicylhydroximate, the structure of the MC can easily be conserved as the identity of the carboxylate is varied. 3,4 A large variety of carboxylate anions have been used including acetate, benzoate, trimethylacetate, hydroxybenzoates (2, 3, and 4 positions), and halogenated benzoates (chloro, bromo, and iodo in the 2, 3, or 4 positions). 3,4 Independent of the identity of the carboxylate anion, the MC has an overall square shape with a Mn–N–O repeat unit about the MC ring, and lanthanide and sodium ions are captured on opposite sides of the central cavity.…”

“…3,4 A large variety of carboxylate anions have been used including acetate, benzoate, trimethylacetate, hydroxybenzoates (2, 3, and 4 positions), and halogenated benzoates (chloro, bromo, and iodo in the 2, 3, or 4 positions). 3,4 Independent of the identity of the carboxylate anion, the MC has an overall square shape with a Mn–N–O repeat unit about the MC ring, and lanthanide and sodium ions are captured on opposite sides of the central cavity. Thus, the properties of these molecules can be finely tuned by the judicious choice of the nature of the carboxylate anions.…”