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oai:figshare.com:article/34020455 2026-09-29T02:04:32Z category_1 category_4 category_19 category_272 category_873 category_39 category_128 category_133 portal_63 item_type_6 month_year_09_2026

Tuning σ‑Hole Chalcogen···Nitrogen Bonding Between C₂F₄Ch₂ and Nitrogen Bases: Dual Modulation by Chalcogen Atomic Size and Nitrogen Hybridization (Ch = S, Se, Te, Po) Ke Peng (2220973) Fengying Lei (4376197) Renhua Chen (627017) Taowang Zhang (25133747) Junhua Chen (1659316) Jinxi Huang (9606655) Qingyu Liu (5332889) Gang Feng (130630) Zuquan Hu (3779044) Tao Lu (39406) Biophysics Biochemistry Pharmacology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Ecology Hematology Plant Biology natural bond orbital largest attractive contribution held together primarily attracted considerable attention interactions remains underexplored electrostatic interactions provide topological analysis indicates nitrogen lone pair nitrogen base sequence distinct hybridization patterns chalcogen bonding interactions partially covalent nature chalcogen ··· nitrogen chalcogen atomic size ch ··· n 2 </ sub 4 </ sub 3 </ sub nh  ch nitrogen hybridization nitrogen bases chalcogen bonds analysis suggests hole interactions − 62 − 16 two moieties shell characteristics recent years prominent subclass pivotal roles interacting partners electrophilic sites electronic structures dual modulation diverse chemical combined influence chbs ), biological systems antibonding orbitals 5 kj Chalcogen bonds (ChBs), a prominent subclass of σ-hole interactions in which Group 16 elements serve as electrophilic sites, have attracted considerable attention in recent years because of their pivotal roles in diverse chemical and biological systems. However, the combined influence of the chalcogen atomic size and the nitrogen atomic hybridization state on the nature and strength of chalcogen···nitrogen (Ch···N) interactions remains underexplored. Herein, σ-hole-type Ch···N ChBs formed between 2,2,4,4-tetrafluoro-1,3-dichalcogenetanes (C₂F₄Ch₂, Ch = S, Se, Te, Po) and nitrogen bases with distinct hybridization patterns (sp-NCH, sp²-NHCH₂, sp²-pyridine, sp³-NH₃) are systematically investigated using quantum chemical calculations. The computed interaction energies vary from −16.8 to −62.5 kJ/mol. The two moieties are held together primarily through the Ch···N ChBs. These ChBs show substantial bond contraction, with Ch···N distances approximately 12–29% shorter than the sum of the respective van der Waals radii. Topological analysis indicates that although most Ch···N ChBs exhibit noncovalent closed-shell characteristics, Te/Po···N ChBs in complexes with NH₃, NHCH₂, or pyridine display a partially covalent nature. Notably, the Ch···N ChB strength typically increases in the order Ch = S < Se < Po < Te and follows the nitrogen base sequence: NCH (sp) < NH₃ (sp³) < NHCH₂ (sp²) < pyridine (sp²). Natural bond orbital (NBO) analysis suggests that the predominant orbital interaction associated with the Ch···N ChB involves charge transfer from the nitrogen lone pair into the σ*(C–Ch) antibonding orbitals. Energy decomposition analysis reveals that electrostatic interactions provide the largest attractive contribution to the stabilization of these chalcogen-bonded complexes. These findings provide critical insights into the tunability of chalcogen bonding interactions by modulating the atomic and electronic structures of the interacting partners. 2026-09-28T00:00:00Z Text Journal contribution 10.1021/acsomega.6c07591.s001 https://figshare.com/articles/journal_contribution/Tuning_Hole_Chalcogen_Nitrogen_Bonding_Between_C_sub_2_sub_F_sub_4_sub_Ch_sub_2_sub_and_Nitrogen_Bases_Dual_Modulation_by_Chalcogen_Atomic_Size_and_Nitrogen_Hybridization_Ch_S_Se_Te_Po_/34020455 CC BY-NC 4.0