Silver Coordination Polymers Based on p-Cyanophenylsilanes as Ligands

• Published in: ChemPlusChem (Weinheim, Germany) Germany), 2014-07, Vol.79 (7), p.973-984
• Main Authors: Blankschein, Bianca, Schulz, Axel, Villinger, Alexander, Wustrack, Ronald
• Format: Article
• Language: English
• Subjects: coordination modes; coordination polymers; salt effect; silver; X-ray diffraction
• ISSN: 2192-6506; 2192-6506
• DOI: 10.1002/cplu.201402026

Differently substituted p‐cyanophenylsilanes, Me4−nSi(C6H4CN)n, (n=2, 3, 4), PhSi(C6H4CN)3, cycHexSi(C6H4CN)3 (cycHex=cyclohexyl), and MePhSi(C6H4CN)2, were prepared and fully characterized. Their coordination behavior was studied by utilizing silver salts of the type AgX (X=O3SCF3−, CO2CF3−), which led to coordination polymers. One‐dimensional chains were observed for the bidentate p‐cyanophenylsilane ligands, whereas two‐ and three‐dimensional networks, including macrometalacycles, were found for the tridentate ligand. Treatment of AgO2CCF3 with the tetradentate ligand Si(C6H4CN)4 led to the formation of a diamond‐like three‐dimensional network with two interpenetrating nets linked by bridging Ag2(CF3CO2)2 dimers. X‐ray structures show a wide range of close Ag⋅⋅⋅Ag distances in the polymers, which are dependent on the ligand and the anion utilized. Cross my polymer with silver: A general synthesis for different p‐cyanophenylsilanes and their application as bi‐, tri and tetradentate ligands in the coordination chemistry of AgIX (X=O3SCF3−, CO2CF3−) is presented. Treatment of AgO2CCF3 with the tetradentate ligand Si(C6H4CN)4 leads to the formation of a diamond‐like 3D network with two interpenetrating nets linked by bridging Ag2(CF3CO2)2 dimers. (see picture).