Polynuclear Silver(I) Triazole Complexes: Ion Conduction and Nanowire Formation in the Mesophase.

Examples of polynuclear metallomesogens are few. Herein,1,2,4-triazole ligands were used to prepare mono- and polynuclear silver(I) triazole metallomesogens. Besides showing an SmA phase in the mesophase, two interesting properties were observed. First, higher ion conductivity is always found for the polynuclear complexes than for the mononuclear complexes with the same anion, an observation contrary to the knowledge that migration of a monomeric cation should be faster than that of a polymeric cation. Second, thermolysis of the polynuclear silver(I) triazole complexes in the assembled mesophase yielded Ag nanowires, in an excellent demonstration of the assembled nature of the polynuclear silver(I) ions in the thermolysis process.

Tetranuclear silver(I) clusters showing high ionic conductivity in a bicontinuous cubic mesophase.

The synthesis and characterization of tetranuclear silver triazole metallomesogens, [Ag4(L(4)-C(n))6][BF4]4 (L(4)-C(n) = 4-alkyl-1,2,4-triazoles where C(n) stands for C(n)H(2n+1) with n = 12, 14, 16, and 18), are reported. Upon heating, a phase transition sequence of Cr → SmC → Cub → SmA → isotropic liquid is observed for all of these compounds. Depending on the alkyl chain length, two types of cubic phases are found in this series of compounds. Those with shorter alkyl chains (n = 12 and 14) exhibit a micellar cubic phase, whereas long alkyl chains (n =16 and 18) show a bicontinuous cubic phase. Superior ionic conductivity at the bicontinuous cubic mesophase for [Ag4(L4-C16)6][BF4]4 is observed because of the presence of a three-dimensional ion-transporting channel. Doping a small amount of AgBF4 enhances the ionic conduction dramatically, presumably via promotion of the migration of Ag(I) ions in the channels.

Vertex and edge truncated octahedron gold crystals. N-alkylimidazole and silver(I) ion controlled morphology transformation.

Two interesting morphology transformations of Au crystals are observed through reacting a mixture of N-alkylimidazole (denoted as C(n)-im, where C(n) = C(n)H(2n+1), and n = 18 and 1), AgNO(3), and HAuCl(4) at 200 degrees C. The long chain C(18)-im with increasing AgNO(3) concentration leads to a progressive truncation of octahedrons at {100} vertices to produce cubes. On the other hand, increasing the concentrations of C(1)-im and AgNO(3), results in a progressive truncation of octahedrons at {110} edges to give rhombic dodecahedrons, which further transform to the unprecedented tetrahexahedrons. The phenomenon could be understood by considering that while both C(18)-im and C(1)-im function as a capping agent with preferential adsorption on Au {111} facets, Ag(+) adsorbs and is subsequently reduced to Ag on Au {110} facets for the sterically demanding C(18)-im, but on the Au {100} facets for C(1)-im. The competition between the growth of the facets protected by imidazole and Ag controls the morphology transformation via truncation of octahedrons at vertices or edges.