In Situ-Generated Metalloligand Strategy for the Rational Design of 3d-3d-4f Metal–Organic Frameworks
Metalloligands offer a powerful strategy for the rational design of lanthanide transition metal frameworks. In this study, we report three brand-new 3d-3d-4f heterometallic clusters: [Ln<sub>4</sub>Cr<sub>4</sub>NiCl(IN)<sub>9</sub>(μ<sub>2</sub>-OH)<sub>4</sub>(μ<sub>3</sub>-OH)<sub>4</sub>(μ<sub>4</sub>-O)<sub>4</sub>(H<sub>2</sub>O)<sub>5</sub>]·4.5H<sub>2</sub>O (Ln = Gd, referred to as <b>1-Gd</b><sub><b>4</b></sub><b>Cr</b><sub><b>4</b></sub><b>Ni</b>; Ln = Eu, referred to as <b>2-Eu</b><sub><b>4</b></sub><b>Cr</b><sub><b>4</b></sub><b>Ni</b>; HIN = isonicotinic acid) and [Dy<sub>3</sub>CrNi(IN)<sub>6</sub>(μ<sub>3</sub>-OH)<sub>4</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)]·8H<sub>2</sub>O (referred to as <b>3-Dy</b><sub><b>3</b></sub><b>CrNi)</b> by precisely controlling reaction temperature and pH. Structural analysis reveals that the planar [NiCl(IN)<sub>4</sub>(H<sub>2</sub>O)]<sup>3-</sup> metalloligand directs <b>1-Gd</b><sub><b>4</b></sub><b>Cr</b><sub><b>4</b></sub><b>Ni</b> and <b>2-Eu</b><sub><b>4</b></sub><b>Cr</b><sub><b>4</b></sub><b>Ni</b> into symmetrical open-network architectures. In contrast, the vertical planar [Ni(C<sub>2</sub>O<sub>4</sub>)<sub>2</sub>(IN)<sub>2</sub>]<sup>4-</sup> metalloligand guides <b>3-Dy</b><sub><b>3</b></sub><b>CrNi</b> to form a high-symmetrical hexagonal-ring lanthanide MOF. Magnetic studies on <b>1-Gd</b><sub><b>4</b></sub><b>Cr</b><sub><b>4</b></sub><b>Ni</b> reveal weak antiferromagnetic interactions, exhibiting a magnetic entropy change of -Δ<i>S</i><sub>m</sub><sup>max</sup> = 20.38 J kg<sup>-1</sup> K<sup>-1</sup> at 3.5 K under Δ<i>H</i> = 7.0 T, highlighting its potential in magnetic refrigeration.
Authors
- Ji‐Lei Wang (ORCID: https://orcid.org/0000-0001-8410-6248)
- Yan Xu (ORCID: https://orcid.org/0000-0001-6059-075X)
- Jianlin Yao (ORCID: https://orcid.org/0000-0002-0344-9984)
- Pinfang Yan
- Qin Wang (ORCID: https://orcid.org/0000-0002-8384-7703)
Institutions
- Nanjing Tech University (CN)
- State Key Laboratory of Materials-Oriented Chemical Engineering
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2025-05-29
- DOI
- https://doi.org/10.1021/acs.inorgchem.5c01750
- Primary Topic
- Metal-Organic Frameworks: Synthesis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Natural Science Foundation of China