[PMo 12 O 40 ] 3– ‐Induced Perhydroxycucurbit[5]uril‐Based Porous Supramolecular Assemblies

We prepared two new types of (HO) 10 Q[5]‐based supramolecular assemblies by using the [PMo 12 O 40 ] 3– anion as a structure inducer. Single‐crystal X‐ray diffraction analysis revealed that these two types of (HO) 10 Q[5]/[PMo 12 O 40 ] 3– hydrides were constructed from (HO) 10 Q[5]/[PMo 12 O 40 ] 3– ‐based 2D networks in which [PMo 12 O 40 ] 3– plays a key rule in attracting (HO) 10 Q[5] molecules through (1) classical hydrogen bonding of the functionalized hydroxy groups on the back of the (HO) 10 Q[5] molecules, (2) unusual hydrogen bonding of the methylene groups on the back of the (HO) 10 Q[5] molecules, and (3) interaction between electron‐deficient carbon sites of the carbonyl groups of the (HO) 10 Q[5] molecules with electron‐rich oxygen sites of the Mo–O groups from the [PMo 12 O 40 ] 3– anions. An additional electrostatic interaction could exist in K + ‐coordinated (HO) 10 Q[5] complexes.