The first 1,4‐distibabenzene‐1,4‐diide compound [(ADC)Sb]₂ (5) based on an anionic dicarbene (ADC) (ADC=PhC{N(Dipp)C}₂, Dipp=2,6‐iPr₂C₆H₃) is reported as a bordeaux‐red solid. Compound 5, featuring a central six‐membered C₄Sb₂ ring with formally Sb^I atoms may be regarded as a base‐stabilized cyclic bis‐stibinidene in which each of the Sb atoms bears two lone‐pairs of electrons. 5 undergoes 2 e‐oxidation with Ph₃C[B(C₆F₅)₄] to afford [(ADC)Sb]₂[B(C₆F₅)₄]₂ (6) as a brick‐red solid. Each of the Sb atoms of 6 has an unpaired electron and a lone‐pair. The broken‐symmetry open‐shell singlet diradical solution for (6)²⁺ is calculated to be 2.13 kcal mol⁻¹ more stable than the closed‐shell singlet. The diradical character of (6)²⁺ according to SS‐CASSCF (state‐specific complete active space self‐consistent field) and UHF (unrestricted Hartree‐Fock) methods amounts to 36 % and 39 %, respectively. Treatments of 6 with (PhE)₂ yield [(ADC)Sb(EPh)]₂[B(C₆F₅)₄]₂ (7‐E) (E=S or Se). Reaction of 5 with (cod)Mo(CO)₄ affords [(ADC)Sb]₂Mo(CO)₄ (8).

A bidentate pnictogen bonding host‐system based on 1,8‐diethynylanthracene was synthesized by a selective tin‐antimony exchange reaction and investigated regarding its ability to act as a Lewis acidic host component for the complexation of Lewis basic or anionic guests. In this work, the novel C≡C−Sb(C ₂ F ₅ ) ₂ unit was established to study the potential of antimony(III) sites as representatives for the scarcely explored pnictogen bonding donors. The capability of this partly fluorinated host system was investigated towards halide anions (Cl ⁻ , Br ⁻ , I ⁻ ), dimethyl chalcogenides Me ₂ Y (Y=O, S, Se, Te), and nitrogen heterocycles (pyridine, pyrimidine). Insights into the adduct formation behavior as well as the bonding situation of such E⋅⋅⋅Sb−C ^F moieties were obtained in solution by means of NMR spectroscopy, in the solid state by X‐ray diffraction, by elemental analyses, and by computational methods (DFT, QTAIM, IQA), respectively.

A tetradentate host system with four CC–Sb(C₂F₅)₂ functions binds halide ions in a distorted square planar coordination. Experimental and calculated structures reveal a complex interplay of attractive pnictogen bonding and Coulomb repulsion.