Programmable Supramolecular Building Blocks: (Perfluoroarene)₂Ch (Ch = S, Se, Te) as Cooperative σ/π-Hole Donors for Noncovalent Binding of Organic and Organometallic Planar π-Systems

Here we establish bis(perfluoropyridyl)chalcogenides, ChPy^F₂ (Ch = S, Se, Te), as a new class of dual-mode donors that exploit cooperative σ- and π-hole interactions for systematic recognition of organic and organometallic planar π-systems. Supramolecular building blocks capable of predictable self-assembly offer versatile platforms for molecular assembly. The programmable nature of these dual-mode donors is demonstrated through their ability to form systematically controlled cocrystal architectures. Through strategic positioning of electron-deficient regions, these molecules achieve simultaneous engagement with π-electron-rich acceptors via both chalcogen bonding and π-stacking pathways. Systematic cocrystallization with organic aromatic hydrocarbons─from electron-rich durene to extended polycyclic systems (naphthalene, phenanthrene, pyrene, triphenylene)─produces seven distinct programmable architectures with predictably controlled coformer ratios. Normalized Ch···C distances systematically decrease from S (Nc 0.90) to Te (Nc 0.81), with interaction energies ranging from −10.9 to −20.4 kcal/mol. DFT calculations confirm that observed supramolecular architectures result from intrinsic cooperative σ/π-hole interactions rather than fortuitous crystal packing. Universal applicability is demonstrated through remarkable structural analogy between organic (phenanthrene·TePy^F₂, pyrene·TePy^F₂, triphenylene·TePy^F₂) and organometallic ([Pt(ppy)(acac)]·TePy^F₂) cocrystals, establishing design principles that transcend the organic-organometallic boundary. Energy decomposition analysis reveals that larger π-surfaces provide enhanced stabilization through augmented dispersion forces.