Dinuclear　Ag(i)　metallamacrocycles　containing　bis-N-heterocyclic　carbene　units　and　calixarene　fragments　[{1,1′-R2-3,3′-CH　2{(p-R1-C6H2OMe)CH2}　m-bisimidazol-2-ylidene}2-Ag2](PF　6)2　(6a-f),　(6a:　m　=　1,　R1　=　Me,　R2　=　Me;　6b:　m　=　1,　R1　=　t-Bu,　R2　=　Me;　6c:　m　=　1,　R　1　=　Me,　R2　=　naphthylmethyl;　6d:　m　=　1,　R1　=　Me,　R2　=　anthrylmethyl;　6e:　m　=　2,　R1　=　Me,　R2　=　anthrylmethyl;　6f:　m　=　3,　R1　=　t-Bu,　R2　=　anthrylmethyl)　were　synthesized　by　reacting　silver　oxide　with　the　corresponding　bis-imidazolium　salts　(5a-f).　Single　crystal　structural　analyses　reveal　that　metallamacrocycles　of　diverse　sizes　consisting　of　two　NHC-Ag(i)-NHC　units　and　two　calixarene　fragments　are　found　in　the　structures　of　these　dinuclear　complexes.　These　complexes　show　different　configurations　with　the　change　of　the　upper-rims　(R1)　of　the　calixarene　fragments　or　N-substituents　(R　2)　of　the　NHC　rings.　The　two　bis-NHC　ligands　in　the　complexes　generally　adopt　trans-conformations　except　for　the　pair　in　6b.　Complexes　6a　and　6c-d,　in　which　R1　are　methyl　groups,　show　rectangular　cavities　in　their　structures.　Complex　6b,　in　which　R1　are　tert-butyl　groups　of　great　steric　hindrance,　adopts　cone　conformation　analogous　to　that　of　the　calixarene.　Interestingly,　cation-π　interactions　are　present　between　Ag(i)　and　the　π-electron　rich　arene　ring　of　R2　in　the　structures　of　complexes　6c-f.　Intermolecular　C-H⋯F　hydrogen　bonds　exist　in　the　crystal　packing　of　all　these　complexes.　Moreover,　intermolecular　Ag⋯Ag　interactions　are　found　in　complex　6a　and　intermolecular　π-π　interactions　are　observed　in　complexes　6c-f.　These　intermolecular　interactions　lead　to　the　formation　of　2D　supramolecular　layers　in　complex　6c　and　3D　supramolecular　networks　in　complexes　6a-b　and　6d-f,　respectively.　The　fluorescent　chemosensing　behaviors　of　these　metallamacrocycles　were　explored　for　some　neutral　molecules.　The　results　showed　that　6d　can　behave　as　an　efficient　fluorescent　chemosensor　for　p-benzoquinone　and　6e-f　exhibit　fluorescent　quenching　behaviors　for　C　60　or　C70　fullerenes.　©　2013　The　Royal　Society　of　Chemistry.