Homonuclear and Heteronuclear Complexes of Calix[4]-&lt;i&gt;bis&lt;/i&gt;-monothiacrown‑5 with Oligomer and Polymer Structures

Homo-\nand heteronuclear complexes (&lt;b&gt;1&lt;/b&gt;–&lt;b&gt;7&lt;/b&gt;)\nof calix[4]-&lt;i&gt;bis&lt;/i&gt;-monothiacrown-5 (&lt;b&gt;L&lt;/b&gt;)\nwith mercury­(II), cadmium­(II), copper­(I), and potassium­(I)\nsalts adopting dimer, tetramer, one-dimensional (1D), and two-dimensional\n(2D) polymer structures with different coordination modes and connectivity\npatterns were prepared and structurally characterized. Reactions of &lt;b&gt;L&lt;/b&gt; with mercury­(II) iodide and mercury­(II) thiocyanate afforded\na dimer complex [Hg&lt;sub&gt;4&lt;/sub&gt;(&lt;b&gt;L&lt;/b&gt;)&lt;sub&gt;2&lt;/sub&gt;I&lt;sub&gt;8&lt;/sub&gt;]·CH&lt;sub&gt;2&lt;/sub&gt;Cl&lt;sub&gt;2&lt;/sub&gt; (&lt;b&gt;1&lt;/b&gt;) and a 1D coordination\npolymer {[Hg&lt;sub&gt;2&lt;/sub&gt;(&lt;b&gt;L&lt;/b&gt;)­(SCN)&lt;sub&gt;4&lt;/sub&gt;]·CH&lt;sub&gt;2&lt;/sub&gt;Cl&lt;sub&gt;2&lt;/sub&gt;}&lt;sub&gt;&lt;i&gt;n&lt;/i&gt;&lt;/sub&gt; (&lt;b&gt;2&lt;/b&gt;), respectively, in which the exocyclic dimercury­(II) complex units\nof &lt;b&gt;L&lt;/b&gt; are doubly linked by the anions. Reactions of &lt;b&gt;L&lt;/b&gt; with cadmium­(II) iodide in the absence and the presence\nof mercury­(II) iodide gave isostructural 1D coordination polymers\n[Cd&lt;sub&gt;2&lt;/sub&gt;(&lt;b&gt;L&lt;/b&gt;)­I&lt;sub&gt;4&lt;/sub&gt;]&lt;sub&gt;&lt;i&gt;n&lt;/i&gt;&lt;/sub&gt; (&lt;b&gt;3&lt;/b&gt;) and {[Cd&lt;sub&gt;2&lt;/sub&gt;(&lt;b&gt;L&lt;/b&gt;)­I&lt;sub&gt;4&lt;/sub&gt;]­[CdHg­(&lt;b&gt;L&lt;/b&gt;)­I&lt;sub&gt;4&lt;/sub&gt;]}&lt;sub&gt;&lt;i&gt;n&lt;/i&gt;&lt;/sub&gt; (&lt;b&gt;4&lt;/b&gt;), respectively. In the isostructure of &lt;b&gt;3&lt;/b&gt; and &lt;b&gt;4&lt;/b&gt;, the ligands are alternately linked by\nthe exocyclic M-I&lt;sub&gt;2&lt;/sub&gt;-M squares via monocadmium­(II)-mediated\nand dicadmium­(II)-mediated modes, respectively. Reaction of &lt;b&gt;L&lt;/b&gt; with copper­(II) thiocyanate in the presence of potassium­(I)\nthiocyanate afforded a discrete complex {[(K&lt;sub&gt;2&lt;/sub&gt;&lt;b&gt;L&lt;/b&gt;)&lt;sub&gt;4&lt;/sub&gt;Cu&lt;sub&gt;6&lt;/sub&gt;(SCN)&lt;sub&gt;10&lt;/sub&gt;]­[K&lt;sub&gt;2&lt;/sub&gt;&lt;b&gt;L&lt;/b&gt;]&lt;sub&gt;2&lt;/sub&gt;[Cu­(SCN)&lt;sub&gt;3&lt;/sub&gt;]&lt;sub&gt;3&lt;/sub&gt;·2CH&lt;sub&gt;2&lt;/sub&gt;Cl&lt;sub&gt;2&lt;/sub&gt;·CH&lt;sub&gt;3&lt;/sub&gt;CN} (&lt;b&gt;5&lt;/b&gt;) consisting\nof three separated parts: dipotassium­(I) tetramer part linked with\na oligomer copper­(I) thiocyanate backbone, dipotassium­(I) monomer\npart, and trithiocyanato copper­(I) complex part. When a mixture of\nmercury­(II) thiocyanate and potassium­(I) thiocyanate was used, a grid-type\n2D heteronuclear polymer complex [Hg&lt;sub&gt;3&lt;/sub&gt;(K&lt;sub&gt;2&lt;/sub&gt;&lt;b&gt;L&lt;/b&gt;)­(SCN)&lt;sub&gt;8&lt;/sub&gt;]&lt;sub&gt;&lt;i&gt;n&lt;/i&gt;&lt;/sub&gt; (&lt;b&gt;6&lt;/b&gt;) in which the 1D mercury­(II) thiocyanato backbones cross-linked\nby endocyclic dipotassium­(I) complex units of &lt;b&gt;L&lt;/b&gt; was isolated.\nOne pot reaction of &lt;b&gt;L&lt;/b&gt; with a mixture of iodide salts\nof potassium­(I), mercury­(II), and cadmium­(II) gave a binary mixed\nproduct of a discrete complex [(K&lt;sub&gt;2&lt;/sub&gt;&lt;b&gt;L&lt;/b&gt;)&lt;sub&gt;2&lt;/sub&gt;(Cd&lt;sub&gt;3&lt;/sub&gt;I&lt;sub&gt;8&lt;/sub&gt;)]­[Cd&lt;sub&gt;4&lt;/sub&gt;I&lt;sub&gt;10&lt;/sub&gt;] (&lt;b&gt;7&lt;/b&gt;) and a heteronuclear 2D network (&lt;b&gt;8&lt;/b&gt;) which can\nbe manually separated because of the colorless platy and orange–yellow\nblock shapes of the crystals, respectively. In &lt;b&gt;7&lt;/b&gt;, the\nendocyclic dipotassium­(I) complex of &lt;b&gt;L&lt;/b&gt; is linked by Cd&lt;sub&gt;3&lt;/sub&gt;I&lt;sub&gt;8&lt;/sub&gt; clusters.

Topic: Metal-Organic Frameworks: Synthesis and Applications
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences