⁷⁷Se and ¹²⁵Te solid-state NMR and X-ray diffraction structural study of chalcogen-bonded 3,4-dicyano-1,2,5-chalcogenodiazole cocrystals

Three novel chalcogen-bonded cocrystals featuring 3,4-dicyano-1,2,5-selenodiazole (C₄N₄Se) or 3,4-dicyano-1,2,5-tellurodiazole (C₄N₄Te) as chalcogen-bond donors and hydroquinone (C₆H₆O₂), tetraphenylphosphonium chloride (C₂₄H₂₀P⁺·Cl⁻) or tetraethylphosphonium chloride (C₈H₂₀P⁺·Cl⁻) as chalcogen-bond acceptors have been prepared and characterized by single-crystal X-ray diffraction (XRD), powder X-ray diffraction and ⁷⁷Se/¹²⁵Te magic-angle spinning solid-state NMR spectroscopy. The single-crystal XRD results show that the chalcogenodiazole molecules interact with the electron donors through two σ-holes on each of the chalcogen atoms, which results in highly directional and moderately strong chalcogen bonds. Powder XRD confirms that the crystalline phases are preserved upon moderate grinding of the samples for solid-state NMR experiments. Measurement of ⁷⁷Se and ¹²⁵Te chemical shift tensors via magic-angle spinning solid-state NMR spectroscopy confirms the number of magnetically unique chalcogen sites in each asymmetric unit and reveals the impact of chalcogen-bond formation on the local electronic structure. These NMR data are further assessed in the context of analogous data for a wider range of crystalline chalcogen-bonded systems.