Porous 3,4-di(3,5-dicarboxyphenyl)phthalate-based Cd²⁺ coordination polymer and its potential applications

Porous coordination polymers with organic aminium as one of the guest species possess a potential application in dye adsorption and white-light material manufacture. Polycarboxylic acid with multiple COOH substituents tends to form this type of porous material (with metal ion). Here the solvothermal self-assembly between Cd²⁺ and a hexacarboxylic acid creates such a porous material [(CH₃)₂NH₂]₆[Cd₃(L)₂]·5DMF·3H₂O (H₆L = 3,4-di(3,5-dicarboxyphenyl)phthalic acid) 1. Total potential guest accessible void volume in 3-D 1 is found to be 4327 Å³. Based on its better porous structure and stability, the ability of 1 to adsorb organic dyes is investigated. It has been proved that (i) 1 can selectively adsorb cationic dyes as Azure A (AA⁺) and/or Methylene Blue (MB⁺), rather than neutral and anionic ones; (ii) the maximum adsorption capacity is 698.2 mg·g^-1 for AA⁺ and 573.2 mg·g^-1 for MB⁺, respectively; and (iii) to the adsorption of AA⁺, it can be recycled for at least five rounds. Also, it is utilized to fabricate the while-light emitting material. Based on the blue-light emission of 1, the trace Eu³⁺ and Tb³⁺ ions are introduced into the pores of 1 successfully, obtaining a white-light emitting material Eu³⁺/Tb³⁺@1 (CIE chromaticity coordinates: (0.33, 0.32)). Meanwhile, Eu³⁺/Tb³⁺@1 is found to be a potential fluorescence photochromic material, showing a yellow-white-blue light emission. According to these investigations, the relationship between material structure and its adsorption property for dyes, the points that should be paid attention to in the construction of white-light emitting materials as well as the potential adsorption mechanism for dyes and rare earth ions are deeply discussed.