TY - JOUR

T1 - Programmable Supramolecular Building Blocks: (Perfluoroarene) 2 Ch (Ch = S, Se, Te) as Cooperative σ/π-Hole Donors for Noncovalent Binding of Organic and Organometallic Planar π-Systems

AU - Smirnov, Andrey S.

AU - Rozhkov, Anton V.

AU - Burguera, Sergi

AU - Frontera, Antonio

AU - Torubaev, Yury V.

AU - Bokach, Nadezhda A.

AU - Kukushkin, Vadim Yu.

PY - 2025/12/22

Y1 - 2025/12/22

N2 - Here we establish bis(perfluoropyridyl)chalcogenides, ChPyF2 (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·TePyF2, pyrene·TePyF2, triphenylene·TePyF2) and organometallic ([Pt(ppy)(acac)]·TePyF2) 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.

AB - Here we establish bis(perfluoropyridyl)chalcogenides, ChPyF2 (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·TePyF2, pyrene·TePyF2, triphenylene·TePyF2) and organometallic ([Pt(ppy)(acac)]·TePyF2) 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.

U2 - 10.1021/acs.cgd.5c01552

DO - 10.1021/acs.cgd.5c01552

M3 - Article

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

ER -