Structure–Property Relationships in a Series of Hybrid Halopyridinium Ruthenium(IV) Halides
Document Type
Journal Article
Role
Author
Published In
Crystal Growth & Design
Volume
26
Issue
6
First Page
2325
Last Page
2338
Publication Date
3-2026
Abstract
The synthesis and characterization of a family of hybrid ruthenium halides are reported, consisting of haloruthenium octahedra (X = Cl, Br) charge-balanced with halopyridinium (XPy; X = H, Cl, Br, I) organic cations that assemble via noncovalent interactions (NCIs) between ion pairs. Diffuse reflectance spectroscopy showed that compounds containing RuBr62– octahedra displayed a lower band gap (1.05 eV < x < 1.08 eV) compared to compounds with RuCl62– octahedra (1.22 eV < x < 1.43 eV). Additionally, computational density functional theory-based natural bonding orbital analysis and density of state methods were used to characterize second-sphere NCI strengths and explicate molecular orbital perturbations to elucidate their influence on Ru–X orbital constructs and in turn rationalize band-gap trends. Analyses showed that ligand-to-metal charge transfer is responsible for the small band-gap energies and are unperturbed by second-sphere interactions. This report serves as a platform for probing the relationship between the structural and photophysical properties within the haloruthenium family of low-dimensional transition metal halide perovskite derivatives.
Keywords
Cations, Group 17 compounds, Halogens, Inorganic compounds, Perovskites
Suggested Citation
Guthrie, H. D., Stone, S. R. P. '25, Schofield, M. H., & Cahill, C. L. (2026). Structure–Property Relationships in a Series of Hybrid Halopyridinium Ruthenium(IV) Halides. Crystal Growth & Design, 26(6), 2325–2338. https://doi.org/10.1021/acs.cgd.5c01654
Comments
Author's manuscript freely available via the Department of Energy.