The first example of micro-adjustments of a metal organic framework (MOF) structure was observed in a new Zn(ii) MOF (Zn-BTDC-M1) derived from a benzothiadiazole-4,7-dicarboxylic acid (HBTDC) ligand using a light-driven decarboxylation process. Interestingly, such decarboxylation occurs at the non-chelated wing of the ligand, which induced a change in the capability of the MOF for physical N adsorption and chemical NH gas adsorption.
On the basis of the same benzothiadiazole (BTD) ligand 2,1,3-benzothiadiazole-4,7-dicarboxylic acid (HL), two new isomers of three-dimensional (3D) BTD-derived Cd(II) metal-organic frameworks 1-2 {[S@CdL]·xHO} 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@Cd. Each SBU S@Cd is connected by six L 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 HL. 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 slightly distorted octahedral cage in 2), the changes in N adsorption capability and photophysical performance between 1 and 2 are obvious, where 2 shows smaller Brunauer-Emmett-Teller surface area, broader absorption of antidimmer, and longer dual-emission lifetimes. Interestingly, either 1 or 2, the dual emission was clearly red-shifted by increasing the solvent polarity or the acidity of ambience, respectively.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.