A Multifunctional Nanocage-based MOF with Tri- and Tetranuclear Zinc Cluster Secondary Building Units

A new Zn-cluster based MOF, [Zn(21)(BTC)(11)(μ(3)-OH)(3)(μ(4)-O)(3)(H(2)O)(18)]·21EtOH (1) (H(3)BTC = 1,3,5-benzenetricarboxylic acid), with two different types of cluster nodes has been successfully synthesized from Zn(2+) and H(3)BTC under the solvothermal conditions. Single crystal X-ray diffraction studies reveal that 1 is a 3D trinodal (3,5,6)-c framework which features a large octahedral cage organized by nine Zn(3)O and nine Zn(4)O clusters SBUs and twenty-four triangular BTC(3−) linkers. The Eu(3+)/Tb(3+)-incorporated derivative of 1 with 0.251% Eu(3+) and 0.269% Tb(3+) exhibits tunable luminescence from yellow to white and then to blue-green by changing the excitation wavelength from 308 to 315 nm. Metal ion exchange with Cu(2+) affords isomorphous Cu-based MOF with enhanced N(2) and CO(2) adsorption capacity. In addition, 1 can act as a selective luminescent sensor for Cu(2+) and Al(3+) ions.