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Structure−Property Relationships in a Series of Hybrid Halopyridinium Ruthenium(IV) Halides

Guthrie, Haley Dawn [The George Washington University, Washington, DC (United States)] (ORCID:0009000342619469)·Stone, Samuel R.P. [Haverford College, PA (United States)] (ORCID:0009000125454469)·Schofield, Mark H. [The George Washington University, Washington, DC (United States)] (ORCID:0000000296017186)·Cahill, Christopher L. [The George Washington University, Washington, DC (United States)] (ORCID:0000000220153595)
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Abstract

Reported is the synthesis and characterization of a family of hybrid ruthenium halides consisting of haloruthenium octahedra (X = Cl, Br) charge balanced with halopyridinium (XPy; X= H, Cl, Br, I) organic cations which assemble via noncovalent interactions between ion pairs. Diffuse reflectance spectroscopy showed that compounds containing RuBr 6 2- octahedra displayed a lower bandgap (1.05 eV< x < 1.08 eV) compared to compounds with RuCl 6 2- octahedra (1.22 eV < x < 1.43 eV). Additionally, computational density functional theory (DFT) based natural bonding orbital (NBO) analysis and density of state (DOS) methods were used to characterize second-sphere non-covalent interaction strengths and elucidate molecular orbital perturbations to elucidate their influence on Ru-X orbital constructs and in turn rationalize band gap trends. Analyses showed ligand to metal charge transfer is responsible for the small bandgap energies and are unperturbed by second-sphere interactions. Here, 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 perovskites.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYCationsGroup 17 compoundsHalogensInorganic compoundsPerovskites

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Guthrie, Haley Dawn [The George Washington University, Washington, DC (United States)] (ORCID:0009000342619469), Stone, Samuel R.P. [Haverford College, PA (United States)] (ORCID:0009000125454469), Schofield, Mark H. [The George Washington University, Washington, DC (United States)] (ORCID:0000000296017186), Cahill, Christopher L. [The George Washington University, Washington, DC (United States)] (ORCID:0000000220153595). 2026-02-25. Structure−Property Relationships in a Series of Hybrid Halopyridinium Ruthenium(IV) Halides. https://doi.org/10.1021/acs.cgd.5c01654

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