We report the synthesis of two [2]catenane-containing struts which react in the presence of Cu(NO3)2�2.5H2O to yield Cu-paddlewheel-based MOF-1050 and MOF-1051. The solid-state structures of these MOFs reveal that the metal clusters serve to join the heptaphenylene struts into grid-like 2D networks. These 2D sheets are then held together by infinite donor�acceptor stacks involving the [2]catenanes to produce interpenetrated 3D architectures. As a consequence of the planar chirality associated with both the DNP and hydroquinone (HQ) units present in the crown ether, each catenane can exist as four stereoisomers. In the case of the nondegenerate (bistable) catenane, the situation is further complicated by the presence of translational isomers. Upon crystallization, however, only two of the four possible stereoisomers�namely, the enantiomeric (RR) and (SS) forms�and one of the translational isomers, in the case of MOF-1051, are observed in the crystals. The overall topologies of MOF-1050 and MOF-1051, and the selective formation of stereo- and translational isomers during the crystallization, provide evidence that weak noncovalent bonding interactions play a significant role in the assembly of these MOF-like extended (super)structures.

Stereochemical expression of molecular recognition in the formation of extended structures

246th National Meeting (2013)

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