Highly Interpenetrated Supramolecular Networks Supported by N⋅⋅⋅I Halogen Bonding

Abstract
Halogen bonding (XB) has been used to assemble tetrakis(4‐pyridyl)pentaerythritol (tetradentate XB acceptor) with different α,ω‐diiodoperfluoroalkanes (bidentate XB donors) or tetrakis(4‐iodotetrafluorophenyl)pentaerythritol (tetradentate XB donor). The remarkable linearity of the XB formed, the rodlike character of α,ω‐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 44 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.

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