College of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, Hubei 430074, P. R. China.
Inorg Chem. 2011 Sep 19;50(18):9097-105. doi: 10.1021/ic2012809. Epub 2011 Aug 22.
Three phenylethynes bearing methyl carboxylate (HL1), monocarboxylate (H(2)L2), and dicarboxylate (H(2)L3) groups were utilized as ligands to synthesize a new class of organometallic silver(I)-ethynide complexes as bifunctional building units to assemble silver(I)-organic networks. X-ray crystallographic studies revealed that in Ag(2)(L1)(2)·AgNO(3) (1) (L1= 4-C(2)C(6)H(4)CO(2)CH(3)), one ethynide group interacts with three silver ions to form a complex unit. These units aggregate by sharing silver ions with the other three units to afford a silver column, which are further linked through argentophilic interaction to generate a two-demensional (2D) silver(I) network. In Ag(2)(L2)·3AgNO(3)·H(2)O (2) (L2 = 4-CO(2)C(6)H(4)C(2)), the ethynide group coordinates to four silver ions to form a building unit (Ag(4)C(2)C(6)H(4)CO(2)), which interacts through silver(I)-carboxylate coordination bonds to generate a wave-like 2D network and is subsequently connected by nitrate anions as bridging ligands to afford a three-demensional (3D) network. In Ag(3)(L3)·AgNO(3) (3) (L3 = 3,5-(CO(2))(2)C(6)H(3)C(2)), the building unit (Ag(4)C(2)C(6)H(3)(CO(2))(2)) aggregates to form a dimer [Ag(8)(L3)(2)] through argentophilic interaction. The dimeric units interact through silver(I)-carboxylate coordination bonds to directly generate a 3D network. The obtained results showed that as a building unit, silver(I)-ethynide complexes bearing carboxylate groups exhibit diverse binding modes, and an increase in the number of carboxylate groups in the silver(I)-ethynide complex unit leads to higher level architectures. In the solid state, all of the complexes (1, 2, and 3) are photoluminescent at room temperature.
三种带有甲酯（HL1）、单羧酸盐（H2L2）和二羧酸盐（H2L3）基团的苯乙炔被用作配体，合成了一类新型的银（I）-乙炔化物有机金属配合物作为双功能构建单元来组装银（I）-有机网络。X 射线晶体学研究表明，在[Ag2（L1）2·AgNO3]（∞）（1）（L1=4-C2C6H4CO2CH3）中，一个乙炔基团与三个银离子相互作用形成一个配合物单元。这些单元通过与其他三个单元共享银离子聚集在一起，形成一个银柱，然后通过银的相互作用进一步连接，生成一个二维（2D）银（I）网络。在[Ag2（L2）·3AgNO3·H2O]（∞）（2）（L2=4-CO2C6H4C2）中，乙炔基团与四个银离子配位形成一个构筑单元（Ag4C2C6H4CO2），它通过银（I）-羧酸盐配位键相互作用生成一个波浪状的 2D 网络，然后通过硝酸盐阴离子作为桥联配体连接，生成一个三维（3D）网络。在[Ag3（L3）·AgNO3]（∞）（3）（L3=3,5-（CO2）2C6H3C2）中，构筑单元（Ag4C2C6H3（CO2）2）通过银的相互作用聚集形成二聚体[Ag8（L3）2]。二聚体单元通过银（I）-羧酸盐配位键相互作用直接生成一个 3D 网络。所得结果表明，作为一个构筑单元，带有羧酸盐基团的银（I）-乙炔配合物具有多种结合模式，银（I）-乙炔配合物单元中羧酸盐基团数量的增加导致更高层次的结构。在固态中，所有的配合物（1、2 和 3）在室温下都具有光致发光性。
