2D and 3D Anilato-Based Heterometallic M(I)M(III) Lattices: The Missing Link

Area of Science:

• Materials Science
• Coordination Chemistry
• Crystallography

Background:

• Oxalato ligands are known to form heterometallic lattices with M(I) and M(III) ions.
• Anilato-type ligands, structurally similar to oxalato, have not been previously utilized for creating such 2D and 3D lattices.
• The development of new metal-organic frameworks with tunable properties is an active area of research.

Purpose of the Study:

• To synthesize the first 2D and 3D heterometallic lattices utilizing anilato ligands.
• To explore the structural diversity and magnetic properties of these novel anilato-based compounds.
• To compare the lattice formation capabilities of anilato ligands with those of oxalato ligands.

Main Methods:

• Synthesis of novel heterometallic lattices using alkaline metal ions and magnetic chiral tris(anilato)metalate molecular building blocks: [M(III)(C6O4X2)3](3-).
• Characterization of two 2D lattices ((PBu3Me)2[NaCr(C6O4Br2)3] and (PPh3Et)2[KFe(C6O4Cl2)3](dmf)2) and two 3D lattices ((NEt3Me)[Na(dmf)][NaFe(C6O4Cl2)3] and (NBu3Me)2[NaCr(C6O4Br2)3]).
• Investigation of magnetic properties, including paramagnetic behavior and zero-field splitting (ZFS), for selected compounds.

Main Results:

• Successful synthesis of the first 2D and 3D heterometallic lattices incorporating anilato ligands.
• Formation of hexagonal honeycomb layers in 2D lattices and interconnected 3D structures, including interlocked chiral lattices.
• Observation of expected paramagnetic behavior in compounds 1, 3, and 4', consistent with simple monomer models and ZFS parameters for Cr(III) and Fe(III).

Conclusions:

• Anilato ligands can effectively form diverse 2D and 3D heterometallic lattices, analogous to oxalato ligands.
• The synthesized compounds represent new additions to the field of metal-organic frameworks with potential magnetic applications.
• The study demonstrates the versatility of anilato ligands in constructing complex coordination structures.