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
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Diverse Scientific and Economic Studies
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article
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article

Axial Carbonate-BridgedDy2 Complexes HavingRigid N3O2 Equatorial Planes: Stepwise Boostingand Tuning of the Zero-Field SMM Behavior

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Diverse Scientific and Economic Studies
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Axial Carbonate-BridgedDy2 Complexes HavingRigid N3O2 Equatorial Planes: Stepwise Boostingand Tuning of the Zero-Field SMM Behavior

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Abstract

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.

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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 · Figshare (2025) | TGRS Research Map | TGRS