Beschreibung:
<jats:title>Abstract</jats:title><jats:p>To study the interplay between the steric demand of the guest and the space available at the host, we have prepared the tetraammonium complexes {(NH<jats:sub>4</jats:sub>)<jats:sub>4</jats:sub>∩[Mg<jats:sub>4</jats:sub>(L<jats:sup>1/2</jats:sup>)<jats:sub>6</jats:sub>]} <jats:bold>1</jats:bold>, tetrakis(methylammonium) complexes {(Me‐NH<jats:sub>3</jats:sub>)<jats:sub>4</jats:sub>∩[Mg<jats:sub>4</jats:sub>(L<jats:sup>1/2</jats:sup>)<jats:sub>6</jats:sub>]} <jats:bold>2</jats:bold>, tetrakis(ethylammonium) complex {(Et‐NH<jats:sub>3</jats:sub>)<jats:sub>4</jats:sub>∩[Mg<jats:sub>4</jats:sub>(L<jats:sup>1</jats:sup>)<jats:sub>6</jats:sub>]} <jats:bold>3</jats:bold>, and mixed sodium tris(ethylammonium) complex {Na(Et‐NH<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>∩[Mg<jats:sub>4</jats:sub>(L<jats:sup>2</jats:sup>)<jats:sub>6</jats:sub>]} <jats:bold>4</jats:bold>. The tetrahemispheraplexes <jats:bold>1−4</jats:bold> were available in one‐pot syntheses. The tetrakis(alkylammonium) clusters {(R<jats:sup>1</jats:sup>−NH<jats:sub>3</jats:sub>)<jats:sub>4</jats:sub>∩[Mg<jats:sub>4</jats:sub>(L<jats:sup>1</jats:sup>)<jats:sub>6</jats:sub>]} <jats:bold>5</jats:bold> and the mixed diammonium‐bis(<jats:italic>p</jats:italic>‐methoxybenzylammonium) cluster {(NH<jats:sub>4</jats:sub>)<jats:sub>2</jats:sub>(R<jats:sup>2</jats:sup>−NH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>∩[Mg<jats:sub>4</jats:sub>(L<jats:sup>1</jats:sup>)<jats:sub>6</jats:sub>]} <jats:bold>6</jats:bold>, however, were prepared by exchange of the ammonium ions of <jats:bold>1a</jats:bold> by alkylammonium ions. Similarly, exchange of the four ammonium ions of <jats:bold>1b</jats:bold> by alkaline metal cations afforded the tetraalkaline metal tetrahemispheraplexes {M<jats:sub>4</jats:sub>∩[Mg<jats:sub>4</jats:sub>(L<jats:sup>2</jats:sup>)<jats:sub>6</jats:sub>]} <jats:bold>7</jats:bold>.</jats:p>