School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China.
State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210023, China.
Molecules. 2022 Jun 23;27(13):4052. doi: 10.3390/molecules27134052.
Metal-organic frameworks (MOFs) constructed by tetrathiafulvalene-tetrabenzoate (HTTFTB) have been widely studied in porous materials, while the studies of other TTFTB derivatives are rare. Herein, the meta derivative of the frequently used -HTTFTB ligand, -HTTFTB, and lanthanide (Ln) metal ions (Tb, Er, and Gd) were assembled into three novel MOFs. Compared with the reported porous Ln-TTFTB, the resulted three-dimensional frameworks, Ln--TTFTB ([Ln(-TTFTB)(-HTTFTB)(HCOO)(DMF)]·2DMF·3HO), possess a more dense stacking which leads to scarce porosity. The solid-state cyclic voltammetry studies revealed that these MOFs show similar redox activity with two reversible one-electron processes at 0.21 and 0.48 V (vs. Fc/Fc). The results of magnetic properties suggested Dy--TTFTB and Er--TTFTB exhibit slow relaxation of the magnetization. Porosity was not found in these materials, which is probably due to the meta-configuration of the -TTFTB ligand that seems to hinder the formation of pores. However, the -TTFTB ligand has shown to be promising to construct redox-active or electrically conductive MOFs in future work.
四硫富瓦烯-四苯甲酸（HTTFTB）构建的金属-有机骨架（MOFs）在多孔材料中得到了广泛的研究，而其他 TTFTB 衍生物的研究则很少。在此，我们将常用的 -HTTFTB 配体的间位衍生物，-HTTFTB，与镧系金属离子（Tb、Er 和 Gd）组装成三种新型 MOFs。与报道的多孔 Ln-TTFTB 相比，所得的三维框架 Ln--TTFTB([Ln(-TTFTB)(-HTTFTB)(HCOO)(DMF)]·2DMF·3HO)具有更密集的堆积，导致孔隙率稀少。固态循环伏安法研究表明，这些 MOFs 具有相似的氧化还原活性，在 0.21 和 0.48 V（相对于 Fc/Fc）处具有两个可逆的单电子过程。磁性研究结果表明 Dy--TTFTB 和 Er--TTFTB 表现出磁化的缓慢弛豫。在这些材料中没有发现孔隙率，这可能是由于 -TTFTB 配体的间位构型似乎阻碍了孔隙的形成。然而，-TTFTB 配体有望在未来的工作中构建氧化还原活性或导电 MOFs。
