School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, Hubei 430074, PR China.
Dalton Trans. 2013 Mar 28;42(12):4306-12. doi: 10.1039/c2dt32030d.
Two ligands with different geometries have been prepared to synthesize new silver-ethynide complexes bearing pyridyl and carboxylate groups. Reactions of 5-ethynylnicotinic acid (H(2)L1) and 5-ethynylpicolinic acid (H(2)L2) with silver nitrate afforded Ag(2)(L1)·AgNO(3) (1) and {[Ag(12)(L2)(6)·12AgNO(3)]·5H(2)O}(n) (2), respectively. Crystallographic studies revealed that in 1, the L1 ligands connect linear silver chains to form a 2D layer through silver-ethynide interactions and Ag-carboxylate coordination bonds, and subsequently the layers are further linked through Ag-N(pyridyl) coordination bonds to generate a 3D network; however in 2, the L2 ligand interacts with Ag(8) units through Ag-N, Ag-O coordination bonds, silver-ethynide interactions and π-π stacking directly to assemble a 3D network. In the solid state, both complexes are luminescent at room temperature, assigned as the intraligand n-π* and π-π* transitions.
已经制备了两种具有不同几何形状的配体，以合成具有吡啶基和羧酸盐基团的新型银乙炔配合物。5-乙炔基烟酸（H（2）L1）和 5-乙炔基吡啶酸（H（2）L2）与硝酸银反应分别得到[Ag（2）（L1）·AgNO（3）]（n）（1）和{[Ag（12）（L2）（6）·12AgNO（3）]·5H（2）O}（n）（2）。晶体学研究表明，在 1 中，L1 配体通过银乙炔相互作用和 Ag-羧酸盐配位键将线性银链连接形成二维层，然后通过 Ag-N（吡啶基）配位键进一步连接以生成三维网络;然而，在 2 中，L2 配体通过 Ag-N、Ag-O 配位键、银乙炔相互作用和π-π堆积直接与 Ag（8）单元相互作用，组装成三维网络。在固态下，两个配合物在室温下均具有发光性，可归因于内配体 n-π和π-π跃迁。
