Topotactic Conversion of Titanium-Oxo Clusters to a Stable TOC-Based Metal-Organic Framework with the Selective Adsorption of Cationic Dyes
Chen-Yue Luo, Li-Jun Ma, Wei Liu, Yu-Chuan Tan, Ruo-Nan Wang, Jin-Le Hou, and Qin-Yu Zhu*(朱琴玉)
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123,P. R. China
Inorg. Chem.2024, 63, 13, 5961-5971
Abstract:Titanium-oxo cluster (TOC)-based metal-organic frameworks (MOFs) have received considerable attention in recent years due to their ability to expand the application of TOCs to fields that require highly stable frameworks. Herein, a new cyclic TOC formulated as [Ti6O6((OiPr)8(TTFTC)(phen)2]2(1, where TTFTC = tetrathiafulvalene tetracarboxylate and phen = phenanthroline) was crystallographically characterized. TOC1takes a rectangular ring structure with two phen-modified Ti6clusters as the width and two TTFTC ligands as the length. An intracluster ligand-to-ligand (TTF-to-phen) charge transfer in1was found for TOCs for the first time. Compound 1 undergoes topotactic conversion to generate stable TOC-MOFP1, in which the rectangular framework in1formed by a TOC core and ligands is retained, as verified by comprehensive characterization.P1shows an efficient and rapid selective adsorption capacity for cationic dyes. The experimental adsorption capacity (qex) ofP1reaches a value of up to 789.2 mg/g at 298 K for the crystal violet dye, which is the highest among those of various adsorbents. The calculated models are first used to reveal the structure-property relationship of the cyclic host to different guest dyes. The results further confirmed the host MOF structure ofP1.
链接：https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c04608
