Synthetic Considerations in the Self-Assembly of Coordination Polymers of Pyridine-Functionalized Hybrid Mn-Anderson Polyoxometalates

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The incorporation of polyoxometalates (POMs) as structural units into ordered porous constructs such as metal–organic frameworks (MOFs) is desirable for a range of applications where intrinsic properties inherited from both the MOF and POM are utilized, including catalysis and magnetic data storage. The controlled self-assembly of targeted MOF topologies containing POM units is hampered by the wide range of oxo and hydroxo units on the peripheries of POMs that can act as coordinating groups toward linking metal cations leading to a diverse range of structures, but incorporation of organic donor units into hybrid POMs offers an alternative methodology to programmably synthesize POM/MOF conjugates. Herein, we report six coordination polymers obtained serendipitously wherein Zn 2+ and Cu 2+ link pyridine-appended Mn-Anderson clusters into two- and three-dimensional network solids with complex connectivities and topologies. Careful inspection of their solid-state structures has allowed us to identify common structure-directing features across these coordination polymers, including a square motif where two Zn 2+ cations bridge two POMs. By correlating certain structural motifs with synthetic conditions, we have formulated a series of design considerations for the self-assembly of coordination polymers of hybrid POMs, encompassing the selection of reaction conditions, coligands, and linking metal cations. We anticipate that these synthetic guidelines will inform the future assembly of hybrid POMs into functional MOF materials.