The dibenzimidazolium salts bis[N-(alkyl)benzimidazoliumylmethyl]durene·2X (1a: alkyl = C₂H₅, X = Br; 1b: alkyl = C₂H₅, X = PF₆; 1c: alkyl = n-C₃H₇, X = Cl; 1d: alkyl = n-C₄H₉, X = I; 1e: alkyl = 1-PyCH₂, X = Br; durene = 1,2,4,5-tetramethylbenzene) and the diimidazolium salt bis[N-(butyl)imidazoliumylmethyl]durene hexafluorophosphate (1f), and their seven NHC copper(I), mercury(II) and silver(I) complexes, [durene(CH₂bimyEt)₂Cu₂I₂] (2b), [durene(CH₂bimyEt)₂HgBr]·0.5[HgBr₄] (2c), [durene(CH₂bimyⁿBu)₂Hg₂(CHCN)][HgI₄] (2d), [durene(CH₂imyⁿBu)₂Ag₂(CH₂CN)₂] (2e), [durene(CH₂bimyPyCH₂)₂Ag₂Br₂] (2f), [durene(CH₂bimyEt)₂Ag][PF₆] (2g) and [durene(CH₂bimyⁿBu)₂Ag₂(OH)₂] (2h), as well as one anionic complex [durene(CH₂benzimidazoliumylⁿPr)₂][PdCl₃(DMSO)]₂ (2a) (bimy = benzimidazol-2-ylidene, imy = imidazol-2-ylidene), have been prepared and characterized. These compounds adopt two diverse conformations (i.e., cis- and trans-conformations). In 2d and 2e, an interesting phenomenon is that the α-carbon atoms of deprotonated acetonitrile ([CHCN]²⁻ for 2d and [CH₂CN]⁻ for 2e) participate in coordination with metal ions. In the crystal packings of these complexes, 1D supramolecular chains or 2D supramolecular layers are formed via intermolecular weak interactions, including π–π interactions, hydrogen bonds and C–H⋯π contacts.