High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide–Copper 15-Metallacrown-5 Complexes (Ln<sup>III</sup> = Pr, Nd, Sm, Eu)
Bibliographic record
Abstract
Complexes {[LnCu 5 (GlyHA) 5 ( m -bdc)(H 2 O) 4– x ] 2 [LnCu 5 (GlyHA) 5 (SO 4 )( m -bdc)(H 2 O) 4 ] 2 }·(30 + 2 x )H 2 O (where GlyHA 2– = glycinehydroxamate, m -bdc 2– = m -phthalate; Ln = Pr and x = 0.21 for compound 1, or Ln = Sm and x = 0.24 for 3 ) and one-dimensional (1D) coordination polymers {[NdCu 5 (GlyHA) 5 (H 2 O) 5 ( m -bdc)] n n [NdCu 5 (GlyHA) 5 (H 2 O) 4 (μ-CO 3 )( m -bdc)]}·13 n H 2 O ( 2 ) and {[EuCu 5 (GlyHA) 5 (H 2 O) 3 ]( m -bdc) 2 [EuCu 5 (GlyHA) 5 ( m -bdc)(H 2 O) 3 ]} n ·17 n H 2 O ( 4 ) were obtained starting from the 15-metallacrown-5 complexes {[LnCu 5 (GlyHA) 5 (SO 4 )(H 2 O) 6.5 ]} 2 (SO 4 )·6H 2 O (Ln = Pr, Nd, Sm, Eu) by the partial or complete metathesis of sulfate anions with m -phthalate. Compounds 1 and 3 contain unprecedented quadruple-decker neutral metallacrown assemblies, where the [LnCu 5 (GlyHA) 5 ] 3+ cations are linked by m -phthalate dianions. In contrast, in complexes 2 and 4, these components assemble into 1D chains of coordination polymers, the adjacent {[NdCu 5 (GlyHA) 5 (H 2 O) 5 ( m -bdc)] + } n 1D chains in 2 being separated by discrete [NdCu 5 (GlyHA) 5 (H 2 O) 4 (μ-CO 3 )( m -bdc)]} − complex anions. The crystal lattices of 2 and 4 contain voids filled by solvent molecules. Desolvated 4 is able to absorb up to 0.12 cm 3 /g of methanol vapor or 0.04 cm 3 /g of ethanol at 293 K. The isotherm for methanol absorption by compound 4 is consistent with a possible “gate opening” mechanism upon interaction with this substrate. The χ M T vs T data for complexes 1 – 4 and their simpler starting materials {[LnCu 5 (GlyHA) 5 (SO 4 )(H 2 O) 6.5 ]} 2 (SO 4 )·6H 2 O (Ln(III) = Pr, Nd, Sm, Eu) were fitted using an additive model, which takes into account exchange interactions between lanthanide(III) and copper(II) ions in the metallamacrocycles via a molecular field model. The exchange interactions between adjacent Cu(II) ions in metallacrown fragments were found to fall in the range of −47 < J Cu–Cu < −63 cm –1 . These complexes are the first examples of a Ln(III)-Cu(II) 15-metallacrowns-5 (Ln(III) = Pr, Nd, Sm, Eu), for which values of exchange parameters have now been reported.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| 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 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".