Axial Carbonate-BridgedDy<sub>2</sub> Complexes HavingRigid N<sub>3</sub>O<sub>2</sub> Equatorial Planes: Stepwise Boostingand Tuning of the Zero-Field SMM Behavior
Herein, we report the synthesis of carbonate-bridged binuclear Ln(III) complexes [Dy<sub>2</sub>(<b>L</b><sub><b>1</b></sub><sup>2–</sup>)<sub>2</sub>(CO<sub>3</sub><sup>2–</sup>)(MeOH)<sub>2</sub>] complex <b>1-Dy</b><sub><b>2</b></sub>, [Y<sub>2</sub>(<b>L</b><sub><b>1</b></sub><sup>2–</sup>)<sub>2</sub>(CO<sub>3</sub><sup>2–</sup>)(MeOH)<sub>2</sub>] complex <b>1-Y</b><sub><b>2</b></sub>, [Dy<sub>2</sub>(<b>L</b><sub><b>1</b></sub><sup>2–</sup>)<sub>2</sub>(CO<sub>3</sub><sup>2‑</sup>)(MeOH)(TPPO)] complex <b>2-Dy</b><sub><b>2</b></sub>, [Y<sub>2</sub>(<b>L</b><sub><b>1</b></sub><sup>2–</sup>)<sub>2</sub>(CO<sub>3</sub><sup>2–</sup>)(MeOH)(TPPO)] complex <b>2-Y</b><sub><b>2</b></sub>, [Dy<sub>2</sub>(<b>L</b><sub><b>1</b></sub><sup>2–</sup>)<sub>2</sub>(CO<sub>3</sub><sup>2–</sup>)(TPPO)<sub>2</sub>] complex <b>3-Dy</b><sub><b>2</b></sub>, and [Dy<sub>2</sub>(<b>H</b><sub><b>2</b></sub><b>L</b><sub><b>2</b></sub><sup>2–</sup>)<sub>2</sub>(CO<sub>3</sub><sup>2–</sup>)(TPPO)<sub>2</sub>] complex <b>4-Dy</b><sub><b>2</b></sub>, having a rigid equatorial pentagonal plane around each Ln(III) ion. The Schiff base <b>H</b><sub><b>2</b></sub><b>L</b><sub><b>1</b></sub> (2,6-diacetylpyridine bis-benzoyl hydrazone) and <b>H</b><sub><b>4</b></sub><b>L</b><sub><b>2</b></sub> (2,6-diacetylpyridine bis-salicyl hydrazone) ligands were used to provide a rigid equatorial pentagonal plane to the Ln(III) ions through their N<sub>3</sub>O<sub>2</sub> donor atoms. One of the axial sites of each Ln(III) is occupied by triphenylphosphine oxide (TPPO) or methanol ligand, while CO<sub>3</sub><sup>2–</sup> occupies the other axial sites. The successful replacement of axially coordinated methanol by the TPPO ligand boosted the zero-field SMM property in <b>3-Dy</b><sub><b>2</b></sub>. We observed that phenolic −OH in <b>H</b><sub><b>2</b></sub><b>L</b><sub><b>2</b></sub><sup>2–</sup> ligands imposes significant structure orientation in <b>4-Dy</b><sub><b>2</b></sub> compared to <b>3-Dy</b><sub><b>2</b></sub> and tunes the zero-field SMM properties by altering the Dy1-<i>O</i>-Dy2 bridging angle.
Publication Details
- Journal
- Figshare
- Published
- 2025-03-13
- DOI
- https://doi.org/10.1021/acs.cgd.4c01468.s001
- Primary Topic
- Diverse Scientific and Economic Studies
- Type
- article
- Field-Weighted Citation Impact
- 0.00