Exploring the nonlinear optical properties of hypoxanthinium salts: a structural and computational analysis

• Published in: Journal of molecular modeling Vol. 30; no. 8; p. 280
• Main Authors: Athmani, Hamza, Direm, Amani, Osório, Francisco A. P., Valverde, Clodoaldo
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01-08-2024; Springer Nature B.V
• Subjects: Bromine; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Chlorides; Chlorine; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Crystallography; Density functional theory; Hydrogen bonding; Molecular Medicine; Nonlinear optics; Optical properties; Original Paper; Refractivity; Structural analysis; Theoretical and Computational Chemistry; Topological analysis; Hydrogen bonds; Hypoxanthinium salt; analysis; Non-classical interactions; NLO properties; DFT calculations; Crystal structure; HS analysis
• ISSN: 1610-2940; 0948-5023; 0948-5023
• DOI: 10.1007/s00894-024-06077-x

Context
In this study, we detail the synthesis and crystallographic characterization of an unprecedented structure, specifically hypoxanthinium chloride monohydrate ((
I
) hereafter), which crystallizes in the monoclinic
P
2
1
/c space group. A comparative analysis was conducted with four related hypoxanthinium salts: hypoxanthinium bromide monohydrate (
II
), 9-methylhypoxanthinium chloride monohydrate (
III
), hypoxanthinium nitrate monohydrate (
IV
), and hypoxanthinium perchlorate monohydrate (
V
). This analysis has focused mainly on their crystal packing, hydrogen-bonding networks, and non-classical intermolecular interactions, as elucidated by comprehensive
Hirshfeld
surface and topological analyses. Theoretical investigation of the nonlinear optical (NLO) properties of the hypoxanthinium derivatives (
I
–
V
) was performed using the Density Functional Theory (DFT).
Methods
The crystalline environment was simulated using the iterative Supermolecule method (SM), and the static and dynamics linear refractive index, linear polarizability, second-order hyperpolarizability, and the third-order nonlinear susceptibility at the DFT/CAM-B3LYP/6–311++G(
d
,
p
) level were computed. The results for the macroscopic third-order nonlinear susceptibility of (
II
) was found to equal
χ
3
=
0.81
×
10
-
20
m
2
/
V
2
. By replacing the bromine atom in (
II
) with a chlorine atom as in (
III
), the
χ
3
value will be multiplied by 2.16, and therefore these results are large enough to suggest the potential application of these crystals as NLO materials.