Structure and properties of metal–organic frameworks modulated by sulfate ions

Abstract

Anions play a significant role in the construction of metal–organic frameworks (MOFs). Anions can affect coordination between metal ions and organic ligands, and the formation of crystal structures, thereby affecting the structure and properties of MOFs. Two novel 3D porous MOFs ({[Cd₃(TIPE)₂(SO₄)_1.6(H₂O)_2.4]·2.8OH·6.2H₂O}_n (MOF-1) and {[Cd₃(TIPE)₂(SO₄)₃(H₂O)₂]·10H₂O}_n (MOF-2)) were successfully synthesized, by introducing SO₄²⁻ to design and adjust their structure and properties, in which the sulfate ions not only participated in coordination but also played a bridging role. Both MOF-1 and MOF-2 exhibited high stability and strong fluorescence properties, and their fluorescence properties also changed compared to those of previously reported 2D nonporous MOF-3 ({[Cd₂(TIPE)₂Cl₃(ACN)]·CdCl₃·3H₂O}_n) with an identical ligand. They could also be used in combination with MOF-3 to distinguish between Fe³⁺ and Cr₂O₇²⁻ ions, due to a change in their fluorescence properties. In this work, the structure was reshaped by introducing sulfate ions, and the role and function of the sulfate ions in the structure were studied, providing a feasible idea for the design and precise regulation of MOFs.