Abstract
We have synthesized bis(N‐hexylethylenediamine)silver(I) nitrate ([Ag(hex‐en)~2~]NO~3~), bis(N‐octylethylenediamine)silver(I) nitrate ([Ag(oct‐en)~2~]NO~3~), and bis(N‐dodecylethylenediamine)silver(I) nitrate ([Ag(dod‐en)~2~]NO~3~) and investigated the aggregation behavior of [Ag(dod‐en)~2~]NO~3~ and [Ag(oct‐en)~2~]NO~3~ in the liquid state. An X‐ray crystallographic analysis revealed that [Ag(dod‐en)~2~]NO~3~ has a dinuclear structure in the crystalline state — the molecular composition unit is Ag~2~(dod‐en)~4~~2~, where the two dod‐en ligands bridge two silver ions that are coordinated by four nitrogen atoms. The dinuclear complex is appreciably dissociated into a mononuclear complex in solution. It was found that [Ag(oct‐en)~2~]NO~3~ and [Ag(dod‐en)~2~]NO~3~ form thermotropic liquid crystals in the temperature ranges 48−67 °C and 59−96 °C, respectively, and a lyotropic liquid crystal was also observed for [Ag(dod‐en)~2~]NO~3~ in n‐heptane at around room temperature in the presence of a small amount of water. The structures of the thermotropic and lyotropic liquid crystals of [Ag(dod‐en)~2~]NO~3~ were identified as a typical smectic A (S~A~) type and a nematic one, respectively. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)