Dinuclear gold(I) complexes [mu-(4,4'-CN-R-NC){Au(C6F4OC4H9)}(2)] [R = 1,4-phenylene, n = 8; R = 4,4'-biphenylene, 2,2'-dichloro-4,4'-biphenylene, 2,2'-dimethyl-4,4'-biphenylene, n = 4,6,8,10] have been prepared and their liquid crystal behavior and optical properties studied. Although the free ligands are not mesomorphic, all the gold( I) derivatives described, except the phenylisonitrilegold(I) derivative [mu-(1,4-CN-C6H4-NC){Au(C6F4OC8H17)}(2)], display liquid crystal behavior, giving rise to a nematic mesophase. The transition temperatures decrease in the order 4-4'-biphenylene > 2,2'-dichloro-4-4'-biphenylene > 2,2'dimethyl-4-4'-biphenylene. All compounds show photoluminescence in the solid state and in solution. The single-crystal X-ray diffraction structures of [mu-(4,4'-CN-R-NC){ Au(C6F4OCnH2n+1)}(2)] (R = 4-4'-biphenylene and 2,2'-dichloro-4-4'-biphenylene) have been determined confirming the rodlike structure of the molecule, with a linear coordination around the gold atoms. There are Au center dot center dot center dot Au interactions in the 2,2'-dichlorobiphenyl derivative but not in the 4-4'-biphenyl compound.