Self-assembly of silver(I) trifluoromethanesulfonate with the tripodal ligand tris(2-benzimidazolylmethyl)amine (ntb) affords the trinuclear complex [Ag3(ntb)2](CF3SO3)3, which exhibits a rhombohedral network formed from N-H...O hydrogen bonds and weak Ag O interactions linking [Ag3(ntb)2]3 cations with a novel S6-symmetric (CF3SO3)6 cluster consolidated by multiple F...F interactions.

Three angular ditopic ligands (1,3-bis(benzimidazol-1-ylmethyl)-4,6-dimethylbenzene L1, 1,3- bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L2, and 1,4-bis(benzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene L3) and one tripodal ligand 1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L4 have been prepared. Reaction of these shape-specific designed ligands with different metal salts affords a series of discrete molecular architectures: [Ag2L1 2](BF4)2 1, [Ag2L2 2](CF3SO3)2 2, [CF3SO3- Ag2L3 2]-CF3SO3 3, [CF3SO3- Ag2L3 3]CF3SO3 4, [ClO4- Cu2L2 4](ClO4)3 5, [4H2O+ Ni2L24Cl4]

A new unsymmetric tripodal ligand bis(2-benzimidazolylmethyl)(2-pyridylmethyl)amine (L) bearing two kinds of chromophores benzimidazole and pyridine has been synthesized, and two series of lanthanidecomplexes [LnL(NO3)3] C2H5OH (Ln = La, Sm, Eu, Gd, Tb or Tm) and [LnLCl3(H2O)] C2H5OH (Ln = La, Sm, Eu, Tb or Ho) have been characterized by elemental analyses, FAB mass spectra, 1H NMR, conductivity measurements, and IR spectra. The crystal and molecular structures of the three complexes [SmL(NO3)3] C2H5OH 1, [GdL(NO3)3] C2H5OH 2, and [SmLCl3(H2O)] C2H5OH 3 have been determined by X-ray diffraction analysis. 1 and 2 are isomorphous with the central metal ion co-ordinated by the four nitrogen atoms of the ligand and six oxygen atoms of three chelating nitrate groups. In complex 3, besides the four nitrogen atoms of the ligand and three chlorine atoms, there is one H2O molecule co-ordinated. Conductivity studies on the [LnL(NO3)3] C2H5OH complexes in methanol showed that two of the nitrate anions dissociate to give 2 : 1 electrolytes. Comparison of the emission lifetimes of the Eu3 and Tb3 complexes in CH3OH and CD3OD gives the average value for q, the number of co-ordinated methanol molecules, of 3.4, suggesting the formation of species [LnL(NO3)(CH3OH)3][NO3]2. The emission quantum yields of the nitrate-coordinated series are substantially higher than those of the chloride series, as shown by luminescence studies in MeCN.