Assembly Of Organometallic Networks Based On Silver(Ⅰ)3,6-pyrazyldiethynide And4-aldehydebenzethynes Clusters As Building Units

Design and construction of metal-organic frameworks is presently an active researcharea due to their potential applications in gas storage, catalysis,luminescence materialmagnetism and ion exchange. In the past decade there has been a great interest to useorganometallic complexes to construct coordination networks, among which silver(I)aryl-or alkylethynide complexes are also investigated as one kind of novel buildingunits.In recent years,silver-ethynide complexes bearing pyridyl or pyrimidyl groups andcarboxyl groups have been systematically investigated as building units to constructnovel organometallic networks.It has been shown that:N atom in pyridyl ring usuallycoordinates to one silver ion in the complex unit,the increase of ethynyl group attach onpyridyl ring could lead to the construction of higher-dimensional architecture;andphenylethynide ligand bearing carboxyl groups could make a silver(Ⅰ) phenylethynidecomplex unit interact with more silver(Ⅰ) ions,thus lead to diverse and high levelorganometallic architectures.Considering the above,two new ligands (3,6-pyrazyldiethynide(H2L1) and4-ethynylbenzaldehyde(HL2))were designed to synthesize two new silver(Ⅰ)-ethynidescomplexes([Ag2(L1)·3AgNO3]（n1）and [Ag2(L2)2·AgNO3]（n2）.Crystallographic studiesrevealed that:in network1,In solid state, the complex units aggregate through Ag-Ncoordination bonds and silver-ethynide and argentophilic interactions to form thechair-like slides, which are further connected by Ag…Ag interaction to afford novelladder-like2D silver(I) network, and finally linked by nitrate groups as bridging ligandsto generate a3D coordination network.in network2,one ethynide group coordinates tothree silver ions,both silver-ethynide units(CAg3) exhibit a distorted tetrahedralgeometry,where three silver ions are arranged in an asymmetrical triangle pattren.andeach silver-ethynide unit is connected with other three neighboring units by sharing silver ions to a silver column constructed by aggregation of six-members silver column,thesilver column are further linked through Ag…Ag interaction to generate a2D silvernetwork.