Layered V-B-O polyoxometalate nets linked by diethylenetriamine complexes with dangling amine groups

Area of Science:

• Inorganic Chemistry
• Materials Science
• Supramolecular Chemistry

Background:

• Polyoxometalates (POMs) are versatile nanoscale building blocks with diverse applications.
• Layered POM structures offer unique properties for materials design.
• The incorporation of vanadoborate and vanadium borophosphate clusters presents opportunities for novel network architectures.

Purpose of the Study:

• To synthesize and characterize two new layered polyoxometalate (POM) net structures, SUT-12 and SUT-13.
• To investigate the formation and structural features of these POMs, particularly the role of metal-ligand complexes.
• To explore the unusual phenomenon of dangling amine groups in metal complexes within these POMs using computational methods.

Main Methods:

• Boric acid flux method for SUT-12 synthesis.
• Hydrothermal method for SUT-13 synthesis.
• Density Functional Theory (DFT) calculations to study the Cu(DETA)2 complexes in SUT-13.

Main Results:

• SUT-12, the first 2D structure from a V6B20 vanadoborate cluster, was synthesized.
• SUT-13, constructed from V12B6P12 vanadium borophosphate clusters, was synthesized.
• Both structures feature vanadoborate/vanadium borophosphate clusters linked by Zn(DETA)2 or Cu(DETA)2 complexes, exhibiting an unexpected dangling amine group on DETA ligands.

Conclusions:

• The successful synthesis of SUT-12 and SUT-13 expands the library of layered POM structures.
• The observed dangling amine groups represent an abnormal coordination feature in the metal-DETA complexes.
• DFT calculations provide insights into the electronic and structural basis for this unusual phenomenon, aiding in understanding POM assembly and function.