DFT Analysis of Structural, Energetic and Electronic Properties of Doped, Encapsulated, and Decorated First-Row Transition Metals on B12N12 Nanocage: Part 1

• Published in: Journal of inorganic and organometallic polymers and materials Vol. 34; no. 9; pp. 4082 - 4099
• Main Authors: De Sousa Sousa, Natanael, Silva, Adilson Luís Pereira, Silva, Augusto César Azevedo, de Jesus Gomes Varela Júnior, Jaldyr
• Format: Journal Article
• Language: English
• Published: New York Springer US 2024; Springer Nature B.V
• Subjects: Cages; Chemistry; Chemistry and Materials Science; Configurations; Decoration; Density of states; Encapsulation; Inorganic Chemistry; Molecular orbitals; Organic Chemistry; Polymer Sciences; Systems analysis; Transition metals; Electronic properties; First-row transition metals; TM-modified B; N; DFT calculations
• ISSN: 1574-1443; 1574-1451
• DOI: 10.1007/s10904-024-03071-x

The present study explores the modification of B
12
N
12
nanocages with first-row transition metals (3d TM atoms) in the configurations: doped (TMB
11
N
12
, B
12
N
11
TM), decorated (TM@b
64
, TM@b
66
) and encapsulated (TM@B
12
N
12
) by DFT-D3 method at B3LYP/6-31G (d,p) level of theory, revealing enhanced stability and reactivity in decorated systems. Spin multiplicity analysis revealed the most stable spin state for each nanocage, showing that decorated systems are more stable at high spin. During geometry optimization, structural rearrangements were observed, with Cr@B
12
N
12
emerging as the most stable configuration of the series, exhibiting a strong metal/cage affinity. The DOS study showed that modification with TM significantly changes the electronic properties of the nanocage, revealing a reduction in the HOMO–LUMO gap, increased reactivity and offering valuable information for applications in sensing, catalysis and energy storage. The RMSD data show that, in encapsulated systems, the TM moves from the center of mass to establish more intense interactions with the cage, as seen in the bond order analysis and it is also observed that Zn weakly interacts with B
12
N
12
at any of the studied configurations.
Graphical Abstract