A crown ether isocyanide CNR (R = benzo-15-crown-5) has been synthesized by dehydration of the corresponding formamide. Substitution reactions with the appropriate gold(l) precursors afford the luminescent mononuclear derivatives [AuX(CNR)] (X = Cl, C6F5, Br, I), [Au(C6F4OCH2C6H4OCnH2n+1-p)(CNR)] (n = 4, 8, 10, 12), and [Au(C6F4OCH2C6H2-3,4,5-(OCnH2n+1)(3)(CNR)] (n = 4, 8, 12). X-ray diffraction studies of [AuCl(CNR)] show the molecules associated in a tetranuclear manner with an antiparallel orientation and gold-gold distances of 3.420 and 3.427 angstrom (Au... Au... Au angles are 121.2 degrees). These tetranuclear units generate infinite zigzag chains through longer Au... Au distances of 3.746 angstrom and weak C-H... O nonclassic interactions. Nucleophilic attack to the coordinated isocyanide in [AuCl(CNR)] by methanol or a primary amine produces the carbene derivatives [AuCl{C((NHR)(OMe)}] and [AuCl{C(NHR')(NHR)}] (R' = Me, n-Bu). The ether crown in these complexes is able to coordinate sodium from NaClO4, affording the corresponding bimetallic complexes (Na/Au = 1:1). The derivatives containing one alkoxy chain are liquid crystals, displaying a smectic C mesophase (for n > 4), whereas the trialkoxy derivatives display unidentified or smectic C mesophases, depending on the alkyl chain length. After complexation of sodium salts, the mesogenic behavior is lost. All of the derivatives are luminescent at room temperature in the solid state with emission maxima in the range 405-550 nm; they emit at 77 K from 410 to 572 nm. Only the ligand and the fluoroaryl complexes emit in solution at room temperature, but all of the compounds are luminescent at 77 K. Very interestingly, some fluoroaryl derivatives with alkoxy chains are luminescent not only in the solid, and in solution, but also in the mesophase, and in the isotropic liquid at moderate temperatures. These are the first metal complexes ever reported to show luminescence in the isotropic liquid state.