Interplay of Redox Non-Innocence and Symmetry Breaking in a 4d Coordination Framework

Incorporating 4d and 5d metal ions into coordination frameworks offers a powerful route to quantum materials where orbital delocalization and spin–orbit coupling reshape magnetic and electronic ground states. However, such systems remain difficult to access synthetically. Here we report Mo(pyz) 2 I 2, the first pyrazine-bridged square-lattice framework featuring a paramagnetic 4d metal center, obtained using a new organometallic precursor route that enables Mo incorporation. Structural and spectroscopic data establish a Mo III ({pyz 2 } •– )I 2 formulation and reveal pronounced ligand redox non-innocence accompanied by local symmetry breaking arising from a disordered distribution of neutral and reduced pyrazine linkers─the first experimental observation of local symmetry lowering in a pyrazine-based coordination solid. Magnetic measurements show strong antiferromagnetic interactions without clear evidence of long-range order, and electrical transport indicates narrow-gap semiconducting behavior. Extending pyrazine framework chemistry to the 4d block thus requires new synthetic strategies and reveals new local structural and magnetic degrees of freedom, positioning Mo(pyz) 2 I 2 as a prototype for designing correlated and spin–orbit-entangled states in molecule-based quantum materials based on heavier transition metals.