10.1021/ic034454j.s007
Xian-He Bu
Xian-He
Bu
Ya-Bo Xie
Ya-Bo
Xie
Jian-Rong Li
Jian-Rong
Li
Ruo-Hua Zhang
Ruo-Hua
Zhang
Adjusting the Frameworks of Silver(I) Complexes with New Pyridyl
Thioethers by Varying the Chain Lengths of Ligand Spacers, Solvents,
and Counteranions
American Chemical Society
2003
pyridyl thioether ligands
coordination modes
New Pyridyl Thioethers
coordination geometries
ClO
6 show counteranion effects
CF
Ag 2 L 4
terminal pyridylsulfanyl groups
2003-10-11 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Adjusting_the_Frameworks_of_Silver_I_Complexes_with_New_Pyridyl_Thioethers_by_Varying_the_Chain_Lengths_of_Ligand_Spacers_Solvents_and_Counteranions/3612702
In our efforts to systematically investigate the effects of the linker units of flexible ligands and other factors on the
structures of Ag<sup>I</sup> complexes with thioethers, five new flexible pyridyl thioether ligands, bis(2-pyridylthio)methane
(<b>L</b><b><sup>1</sup></b><sup></sup>), 1,3-bis(2-pyridylthio)propane (<b>L</b><b><sup>3</sup></b><sup></sup>), 1,4-bis(2-pyridylthio)butane (<b>L</b><b><sup>4</sup></b><sup></sup>), 1,5-bis(2-pyridylthio)pentane (<b>L</b><b><sup>5</sup></b><sup></sup>), and 1,6-bis(2-pyridylthio)hexane (<b>L</b><b><sup>6</sup></b><sup></sup>), have been designed and synthesized, and the reactions of these ligands with Ag<sup>I</sup>
salts under varied conditions (varying the solvents and counteranions) lead to the formation of eight novel metal−organic coordination architectures from di- and trinuclear species to two-dimensional networks: [Ag<sub>3</sub>(<b>L</b><b><sup>1</sup></b><sup></sup>)<sub>2</sub>(ClO<sub>4</sub>)<sub>2</sub>](ClO<sub>4</sub>) (<b>1</b>), {[Ag<b>L</b><b><sup>3</sup></b><sup></sup>](ClO<sub>4</sub>)}<sub>∞</sub> (<b>2</b>), {[Ag<sub>2</sub>(<b>L</b><b><sup>4</sup></b><sup></sup>)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>(CHCl<sub>3</sub>)}<sub>∞</sub> (<b>3</b>), {[Ag<b>L</b><b><sup>4</sup></b><sup></sup>](ClO<sub>4</sub>)(C<sub>3</sub>H<sub>6</sub>O)}<sub>∞</sub> (<b>4</b>), {[Ag<sub>2</sub><b>L</b><b><sup>4</sup></b><sup></sup>](NO<sub>3</sub>)<sub>2</sub>}<sub>∞</sub> (<b>5</b>),
[Ag<sub>2</sub><b>L</b><b><sup>4</sup></b><sup></sup>(CF<sub>3</sub>SO<sub>3</sub>)<sub>2</sub>]<sub>∞</sub> (<b>6</b>), {[Ag<b>L</b><b><sup>5</sup></b><sup></sup>](ClO<sub>4</sub>)(CHCl<sub>3</sub>)}<sub>2</sub> (<b>7</b>), and {[Ag<b>L</b><b><sup>6</sup></b><sup></sup>](ClO<sub>4</sub>)}<sub>∞</sub> (<b>8</b>). All the structures were established by
single-crystal X-ray diffraction analysis. The coordination modes of these ligands were found to vary from <i>N,N</i>-bidentate to <i>N,N,S</i>-tridentate to <i>N,N,S,S</i>-tetradentate modes, while the Ag<sup>I</sup> centers adopt two-, three-, or four-coordination geometries with different coordination environments. The structural differences of <b>1</b>, <b>2</b>, <b>3</b>, <b>7</b>, and <b>8</b>
indicate that the subtle variations on the spacer units can greatly affect the coordination modes of the terminal
pyridylsulfanyl groups and the coordination geometries of Ag<sup>I</sup> ions. The structural differences of <b>3</b> and<b> 4</b> indicate
that solvents also have great influence on the structures of Ag<sup>I</sup> complexes, and the differences between<b> 3</b>,<b> 5</b>, and<b>
6</b> show counteranion effects in polymerization of Ag<sup>I</sup> complexes. The influences of counterions and solvents on the
frameworks of these complexes are probably based upon the flexibility of ligands and the wide coordination geometries
of Ag<sup>I</sup> ions. The results of this study indicate that the frameworks of the Ag<sup>I</sup> complexes with pyridyl dithioethers
could be adjusted by ligand modifications and variations of the complex formation conditions.