Two Coordination Polymers Involving Triangular and Linear Trinuclear Co(II) Clusters Created Via In situ Ligand Synthesis

Two novel 3D metal-organic frameworks with cobalt(II) clusters as nodes and mixed bridging ligands as links, {[Co 3 (OH)(tbip) 2 (Htbip)(dps)(dpds) 0.5 ]} n ( 1 ) and {[Co 2 (H 2 O)(tbip) 2 (dps)]·CH 3 OH·2 H 2 O} 2 n ( 2 ) (dps = 4,4′-dipyridylsulfide, dpds = 4,4′-dipyridyldisulfide, H 2 tbip = 5-tert-butyl isophthalic acid), were obtained from the same reaction mixture but tuned by different hydrothermal temperatures: at 120 °C, product 1 is a 3D MOF based on the novel triangular trinuclear cluster node, whereas at 160 °C, product 2 is a 3D MOF constructed from both a linear trinuclear cluster node and a mononuclear Co II node. The starting dpds reagent was partly converted into dps ligand in 1 and wholly transferred into dps in 2 via new in situ cleavage of both S−S and S−C bonds and temperature-dependent in situ ligand rearrangement of dpds.