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Synthesis, Structural Characterization, and Electronic Structure Analysis of F₂-type Superatomic Molecules.

Manman Zhou¹, Chuanjun Zhou¹, Shuang Chen¹

¹Key Laboratory of Structure and Functional Regulation of Hybrid Materials, Anhui University, Ministry of Education, Institutes of Physical Science and Information Technology, Anhui University, Department of Chemistry and Center for Atomic Engineering of Advanced Materials, Anhui University, Hefei, Anhui 230601, P. R. China.

Inorganic Chemistry

|November 28, 2024

Summary

Researchers synthesized and characterized two novel superatomic molecules, [Au2Ag25(C7H4NOS)13(DPPB)3] and [Au9Ag18(C5H4NS)11(DPPM)5]2+. These molecules exhibit electronic structures analogous to the F2 molecule.

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Area of Science:

Materials Science
Inorganic Chemistry
Computational Chemistry

Background:

Superatomic molecules are an emerging class of materials with unique electronic properties.
Understanding bonding interactions in superatoms is crucial for designing new functional materials.
Previous studies have explored various superatomic structures, but F2-type analogues remain largely uninvestigated.

Purpose of the Study:

To synthesize and characterize novel F2-type superatomic molecules.
To elucidate the structural and electronic properties of these new compounds.
To explore the potential of superatoms as analogues for small molecules.

Main Methods:

Synthesis of two new superatomic molecules: [Au2Ag25(C7H4NOS)13(DPPB)3] and [Au9Ag18(C5H4NS)11(DPPM)5]2+.
Structural characterization using X-ray crystallography.
Electronic structure elucidation via density functional theory (DFT) calculations.
Spectroscopic analysis of electronic absorption characteristics.
Tamm-Dancoff approximation DFT (TDA-DFT) calculations.

Main Results:

Successful synthesis and structural confirmation of two distinct superatomic molecules.
X-ray crystallography revealed horizontal expansion in [Au2Ag25(C7H4NOS)13(DPPB)3] and vertical expansion in [Au9Ag18(C5H4NS)11(DPPM)5]2+.
DFT and TDA-DFT calculations demonstrated that the Au2Ag21(+9) and Au8Ag15(+9) cores exhibit electronic configurations analogous to the F2 molecule.
Spectroscopic data supported the electronic structure findings.

Conclusions:

The study presents the first F2-type superatomic molecules, expanding the known diversity of superatomic structures.
The findings demonstrate the potential of superatoms to mimic the electronic properties of small molecules.
This work opens new avenues for designing superatomic materials with tailored electronic functionalities.