Hierarchy and Synergy of Anion‐π, Hydrogen Bonding and π‐π Interactions in Multicomponent Ionic Hybrid Architectures

The knowledge of different types of anion‐binding modes offered by π‐acidic HAT(CN) 6 and resorcinol‐like double proton donors was successfully applied to construct unprecedented ternary {[HAT(CN) 6 ];[PG];[X – ] 2 } (HAT(CN) 6 = 1,4,5,8,9,12‐hexaazatriphenylene‐hexacarbonitrile, PG = phloroglucinol; X = Cl, Br) synthons both in the solid state and in solution. These systems feature an adaptative coexistence of anion‐π, hydrogen bonding, and π‐π interactions, all supported by multiple phenyl embraces of PPh 4 + cations. The key contributing motifs ‐ {[HAT(CN) 6 ];[X – ] 2 }, {[PG];[X – ] 2 }, and {[HAT(CN) 6 ];[PG]} ‐ successfully followed the patterns observed in related binary systems. Combined experimental‐computational SC XRD, UV‐Vis, NMR ( 1 H, 13 C, and 81 Br), and quantum‐chemical approaches disclosed a progressive and hierarchical structural build‐up with clear signatures of synergistic effects involving all three interactions and a well‐defined role of each interaction type in synthons stabilization and shaping intermolecular charge‐transfer properties within the studied adducts. This work introduces a new library of multicomponent ionic systems, paving the way for the future development of extended topological molecular organic‐inorganic architectures and properties that may be governed by the hierarchy and/or synergy of noncovalent interactions.