Linear Trimer Molecule Formation by Three-Center-Four-Electron Bonding in a Crystalline Solid RuP

Some inorganic solids undergo phase transitions that result in the formation of "molecules" in their crystalline frameworks, which are frequently accompanied by dramatic changes in physical properties; the metal-insulator transition (MIT) in vanadium dioxide, for instance, is accompanied by the formation of dimer molecules with conventional two-center-two-electron bonding. We have discovered the creation of a linear ruthenium trimer with atypical three-center-four-electron bonding in ruthenium monophosphide at its MIT. Our detailed structural investigation and electronic structure calculations reveal that charge transfer from polymerized phosphorous to ruthenium automatically tunes the electron density to precisely four per trimer at the MIT, with all conduction electrons present at high temperatures being trapped by the trimer's molecular orbitals at low temperatures. Our results demonstrate that molecules are essential even in solid crystals, as they impact their electronic properties.