Four alkaline earth metal (Mg, Ca, Sr, Ba)-based MOFs as multiresponsive fluorescent sensors for Fe3+, Pb2+ and Cu2+ ions in aqueous solution

Abstract

A series of new alkaline earth-metal organic frameworks (AE-MOFs), i.e. {[Mg2(μ6-L)(μ2-OH2)(H2O)4]·DMF}n (1), [Ca2(μ10-L)(EtOH)]n (2), [Sr(μ6-H2L)(MeOH)]n (3) and {[Ba1.5(μ5-H2L)(μ4-H3L)(H2O)3]·2(H2O)}n(4) were synthesized under solvothermal reaction by employing a symmetrical V-shaped multicarboxylic acid ligand H4L (H4L = 5,5′-oxydiisophthalic acid), resulting in versatile coordination modes as well as various topologies. 1 forms a uninodal 4-connected (66)-dia 3D topology based on dinuclear Mg2(COO)2(μ2-OH2) clusters. 2 displays an unprecedented 3-nodal (5,5,10)-connected 3D net with (424·621)(48·62)2 topology based on 1D [Ca(COO)]n chains and dinuclear Ca2(COO)2 clusters. 3 indicates a uninodal 6-connected 3D net with (410·65)-sma topology based on 1D [Sr(COO)]n chains. 4 features a new 4-nodal (4,5,6,6)-connected net with (43·63)2(46·64)2(46·68·8)(46·69)2 topology based on two types of 1D chains. 1-4 show solid-state fluorescent properties at ambient temperature. Especially, 1 and 2 have multiresponsive recognition of Fe3+ and Pb2+ ions, Fe3+ and Cu2+ ions, respectively, while 3 and 4 show single selective detection for Fe3+ ion, signifying that they could be potential fluorescent sensors for specific heavy metal ions in water system. The sensing mechanism has also been discussed in detail.