Three novel organosilver(I) coordination networks constructed from diallylmelamine and polycarboxylates incorporating silver-vinyl bonding.

Diallylmelamine combines with Ag(2)O and auxiliary polycarboxylates to give three stable crystalline network structures, namely, [Ag(2)(dama)(2)(nipt)·H(2)O·C(2)H(5)OH](n) (1), [Ag(2)(dama)(glu)](n) (2), and [Ag(4)(dama)(2)(pma)·2H(2)O](n) (3), (dama = diallylmelamine, H(2)nipt = 5-nitroisophthalic acid, H(2)glu = glutaric acid, H(4)pma = pyromellitic acid), which have been successfully synthesized and characterized by elemental analysis, FT-IR Spectra, powder X-ray diffraction and thermogravimetric analyses, and single-crystal X-ray diffraction. Complex 1 is a 1D double-chain extended by μ(2)-N,N'-(η(2)-vinyl)-dama and μ(3)-nipt along the b axis. Notably, dama ligands in 1 display two coordination modes (bidentate μ(2)-N,N'-(η(2)-vinyl) and monodentate μ(1)-N) and two different conformations (cis(anti-gauche) and trans(anti-anti)). In 2, a pair of centrosymmetric glu ligands clamp two Ag(I) ions to form a half paddle-wheel [Ag(2)(COO)(2)] secondary building unit (SBU) which is further extended by μ(2)-N,N'-(η(2)-vinyl)-dama to form a 1D tape. Complex 3 is a 2D sheet built from μ(3)-N,N',N''-(η(2)-vinyl)-dama and μ(8)-pma. Interestingly, apparent silver-vinyl interactions with a η(2) mode were commonly observed in the solid-state structures of 1-3 (Ag-C = 2.311(4)-2.467(5) Å). The structural dissimilarity between 1 and 2 is caused by the different auxiliary polycarboxylates and different coordination modes of dama. In addition, the thermal stabilities and emissive behaviors of them were also investigated.