Temperature tuned syntheses of two new d10-based Cd(ii) cluster metal–organic frameworks: luminescence sensing and photocatalytic properties

Abstract

The solvothermal reactions of 5,5′-(1,4-phenylenebis(methyleneoxy))diisophthalic acid (H₄L) and the N-donor ancillary ligand 3,3′,5,5′-tetramethyl-4,4′-bipyrazole (bpz) with cadmium(II) salts at two different reaction temperatures yielded two new metal–organic frameworks (MOFs), viz., [Cd(H₂L)(bpz)]_n (1) and [Cd₂(H₄L)(L)(bpz)₂]_n (2), which have been characterized by FTIR and single crystal X-ray diffraction. The single crystal X-ray diffraction studies revealed that 1 displays a 3-periodic network with monometallic SBU, while 2 exhibits a 3-periodic network with a 2-fold interpenetration feature. The effects of variation in reaction temperature on the architecture of MOFs 1 and 2 have been discussed. The luminescence investigation indicates that both 1 and 2 displayed good turn-off luminescence sensing against nitroaromatic compounds (NACs), especially m-nitrophenol (MNP), via a decrease in their luminescence intensities with a K_sv value of 6.43 × 10³ for 1 and 2.03 × 10⁴ for 2 and LOD values of 1.09 and 0.81 ppm for 1 and 2, respectively. The plausible mechanism for the decline in luminescence intensity of the MOFs with NACs has been addressed using theoretical calculations. The photocatalytic properties for both the MOFs demonstrated that they display efficient photocatalytic performances to degrade methyl violet (MV) under UV irradiation. The plausible mechanism through which these MOFs exhibited photocatalytic properties has been suggested using band gap calculations.