A symmetric, triply interlaced 3-D anionic MOF that exhibits both magnetic order and SMM behaviourElectronic supplementary information (ESI) available: Synthetic procedure, IR spectrum, TGA trace, additional magnetic data, crystallographic details and additional structural graphic. CCDC 1487245. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6dt02652d

A newly prepared 3-D polymer of cobalt citrate cubanes bridged by high-spin Co( ii ) centres displays both single-molecule magnet (SMM) behaviour and magnetic ordering. Triple interpenetration of the 3-D diamondoid polymers yields a crystalline solid with channels that host cations and free water molecules, with the SMM behaviour of the Co 4 O 4 cores preserved. The octahedrally coordinated Co( ii ) bridges are implicated in the onset of magnetic order at an experimentally accessible temperature. Triply interpenetrated diamondoid nets of a Co citrate MOF, formed by SMM Co citrate cubanes bridged by six-coordinated Co( ii ), preserve SMM behavior with magnetic blocking at 3.8 K, presenting magnetic order at 2.7 K.