The rational design and synthesis of metal-organic frameworks (MOFs) with well-controlled interpenetration represent a significant frontier in materials science, particularly for applications involving porosity and guest-host interactions. In this study, we report the first systematic investigation of interpenetration control in thorium-based MOFs using ligand steric modulation. The inherent “hardness” of the Th⁴⁺ cation, combined with strategic aromatic substitutions and fine-tuned synthetic conditions, enabled the crystallization of seven new thorium MOFs (Th-SINAP-n, n = 16–22) featuring five distinct topologies. Solvothermal reactions between Th(NO₃)₄ and triphenyl H₂TPDC under varying conditions yielded exclusively an interpenetrated framework with a hex topology—designated Th-SINAP-16.1948273-02-6 SMILES Introducing two methyl groups onto the TPDC linker to form 2,5-Me₂TPDC²⁻ and 2,2-Me₂TPDC²⁻ led to two noninterpenetrated UiO-68-type Th-MOFs—Th-SINAP-17 and Th-SINAP-20—both exhibiting record-high pore volumes of 74.8% and 75.3%, respectively, surpassing all previously reported thorium MOFs. Additionally, four more Th-MOFs (Th-SINAP-18, 19, 21, and 22) were obtained via modulated syntheses, revealing three different structural motifs. Notably, Th-SINAP-16 and Th-SINAP-21 are among the rare interpenetrated thorium MOFs documented to date. These results highlight unprecedented structural diversity and synthetic accessibility in Th-MOFs, which stem from the unique soft nature of Th⁴⁺ that facilitates single-crystal formation and enables precise structural tuning. This platform offers a powerful avenue to explore structure-property relationships, especially in iodine adsorption—a critical application for nuclear waste remediation due to the high volatility and biological activity of radioactive iodine isotopes such as ¹²⁹I and ¹³¹I. The slightly radioactive character of thorium is negligible in this context given its much longer half-life (t₁/₂ = 1.405 × 10¹⁰ y) compared to these iodine isotopes. The resulting materials exhibit diverse N₂ and I₂ vapor adsorption capacities, with Th-SINAP-17 showing the highest iodine uptake at 1188 mg/g, correlating strongly with its large void volume and noninterpenetrated architecture.50-02-2 manufacturer In contrast, interpenetrated frameworks like Th-SINAP-16 and Th-SINAP-21 display faster initial adsorption kinetics, suggesting that interpenetration can enhance mass transfer despite reduced pore size.PMID:31424879 Raman spectroscopy confirms charge transfer between electron-rich organic linkers and I₂ molecules, evidenced by characteristic bands at ~108 cm⁻¹ (asymmetric I₃⁻ stretch) and ~165 cm⁻¹ (I₅⁻ signature), supporting strong host-guest interactions. Overall, this work establishes thorium MOFs as a highly tunable and structurally rich class of porous materials, where interpenetration control via ligand engineering provides a viable strategy to optimize performance in iodine capture and other advanced applications.MedChemExpress (MCE) offers a wide range of high-quality research chemicals and biochemicals (novel life-science reagents, reference compounds and natural compounds) for scientific use. We have professionally experienced and friendly staff to meet your needs. We are a competent and trustworthy partner for your research and scientific projects.Related websites: https://www.medchemexpress.com
