The reaction of AuCl(THT) (1) with long chain primary amines (CnH2n+1NH2; n = 8, 12, 16) leads to the formation of the complexes AuCl(NH2R) (R = C8H17, 2; C12H25, 3; C16H33, 4) which are characterized by classical methods and shown to self-organize in the solid state into a fibrous material; decomposition of the complexes inside the supramolecular framework yields a monolayer of ordered gold nanoparticles.