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The use of α,β-unsubstituted dipyrrins, dpm, for the elaboration of infinite architectures in crystalline form based on coordination as well as hydrogen bonding interactions is reviewed. These ligands can be readily functionalized and derivatives bearing either a peripheral hydrogen bond donor/acceptor group or a secondary coordinating group have been developed. In the first case, the complexes incorporating these dpms self-assemble viahydrogen bonding leading to extended architectures. In the second case, the coordinating complexes, or metallatectons, can self-assemble to form homonuclear networks such as in a series of (acac)Cu(dpm) complexes. Upon association of the metallatectons with a second metal centre, heterometallic architectures are formed. These MOFs are constructed by coordination as well as Ag-π interactions depending on the nature of the peripheral coordinating group and the coordination geometry of the metallatecton.
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