[PMo12O40]3–‐Induced Perhydroxycucurbit[5]uril‐Based Porous Supramolecular Assemblies

We prepared two new types of (HO)10Q[5]-based supramolecular assemblies by using the [PMo12O40]3– anion as a structure inducer. Single-crystal X-ray diffraction analysis revealed that these two types of (HO)10Q[5]/[PMo12O40]3– hydrides were constructed from (HO)10Q[5]/[PMo12O40]3–-based 2D networks in which [PMo12O40]3– plays a key rule in attracting (HO)10Q[5] molecules through (1) classical hydrogen bonding of the functionalized hydroxy groups on the back of the (HO)10Q[5] molecules, (2) unusual hydrogen bonding of the methylene groups on the back of the (HO)10Q[5] molecules, and (3) interaction between electron-deficient carbon sites of the carbonyl groups of the (HO)10Q[5] molecules with electron-rich oxygen sites of the Mo–O groups from the [PMo12O40]3– anions. An additional electrostatic interaction could exist in K+-coordinated (HO)10Q[5] complexes.