Highly interpenetrated supramolecular networks supported by N...I halogen bonding.

Halogen bonding (XB) has been used to assemble tetrakis(4-pyridyl)pentaerythritol (tetradentate XB acceptor) with different alpha,omega-diiodoperfluoroalkanes (bidentate XB donors) or tetrakis(4-iodotetrafluorophenyl)pentaerythritol (tetradentate XB donor). The remarkable linearity of the XB formed, the rodlike character of alpha,omega-diiodoperfluoroalkanes and the mutual complementarities of pentaerythritol partners, translate the three-dimensional character of the XB acceptor into open primary networks, which interpenetrate to avoid the presence of voids and to ensure segregation of the modules. Two-dimensional (2D) square 4(4) layers (sql) with fourfold and fivefold interpenetration, as well as an eightfold diamondoid network (dia) of class Ia and a remarkable tenfold dia network of class IIIa, have been obtained.