Two 3D Cd(II) Metal–Organic Frameworks Linked by Benzothiadiazole Dicarboxylates: Fantastic S@Cd6 Cage, Benzothiadiazole Antidimmer, and Dual Emission
2017
On the basis of the same benzothiadiazole (BTD) ligand 2,1,3-benzothiadiazole-4,7-dicarboxylic acid (H2L), two new isomers of three-dimensional (3D) BTD-derived Cd(II) metal–organic frameworks 1-2 {[S@Cd6L6]·xH2O}n were obtained by the different solvothermal reactions, which were structurally similar. Surprisingly, structural analyses reveal that in 1 or 2, one free sulfur atom was fixed in a Cd(II) cluster cage by strong intermolecular interaction to form the secondary building unit (SBU) S@Cd6. Each SBU S@Cd6 is connected by six L2– ligands and further extended into the 3D porous framework. In this work, the BTD antidimmer was evidenced by structural analysis and photophysical study. Furthermore, either 1 or 2 showed the uncommon dual emission, while only one emission was observed in the solution of ligand H2L. The dual-emission mechanism was also realized by the structural analysis and photophysical study. Interestingly, although there is slight difference in structure (regular octahedral cage in 1 and...
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