Molecular Architectures for Trimetallic d/f/d Complexes: Structural and Magnetic Properties of a LnNi<sub>2</sub> Core
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Bibliographic record
Abstract
A series of cationic, trimetallic d/f/d complexes have been prepared which use a multidentate, macrocyclic amine phenol ligand to coordinate divalent first row d-block transition metal ions (TM) and lanthanides (Ln) ions in close proximity, desirable for magnetic studies. Isolable complexes of the d/f/d cluster compounds with the formula [Ln(TM)2(bcn)2]ClO4.nH2O, where H3bcn is tris-N, N', N''-(2-hydroxybenzyl)-1,4,7-triazacyclononane, TM = Zn(II) and Ni(II) and Ln = La(III), Nd(III), Gd(III), Dy(III), and Yb(III), were synthesized by a one-pot sequential reaction of stoichiometric amounts of H 3bcn with the TM(II) and Ln(III) metal ions. The spontaneously formed cationic complexes were characterized by a variety of analytical techniques including IR, NMR, +ESI-MS, and EA. The [TM(Hbcn)].nH2O and [TM3(bcn)2].nH2O complexes were also synthesized to probe the building blocks of the d/f/d coaggregated species. The solid-state X-ray crystal structures of [GdNi2(bcn)2(CH3CN)2]ClO4.CH3CN and [GdZn2(bcn)2(CH3CN)2]ClO4.CH3CN were determined to be nearly identical with each TM(II) encapsulated in an octahedral geometry by the N3O3 binding pocket of the bcn (3-) ligand. The eight coordinate Gd(III) was bicapped by two [TM(bcn)](-) moieties and coordinated by two solvent molecules. Because of the isostructurality of the [LnZn2(bcn)2]ClO4.nH2O and [LnNi2(bcn)2]ClO4.nH2O complexes, an empirical approach using the LnZn2 magnetic data was utilized to remove first-order anisotropic contributions from the LnNi2 species. Ferromagnetic spin interactions were determined for the [LnNi2(bcn)2]ClO4.nH2O complexes, where Ln = Gd(III), Dy(III), and Yb(III), while an antiferromagnetic exchange was observed for Ln = Nd(III).
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Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
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Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
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