Radiation dosimeters displaying conspicuous response of irradiance are highly desirable, owing to the growing demand of monitoring high-energy radiation and environmental exposure. Herein, we present a case of dosimetry based on a discrete nanocluster, [Th6(OH)4(O)4(H2O)6](TPC)8(HCOO)4∙4DMF∙H2O (Th-SINAP-100), by judiciously incorporating heavy Th6 polynuclear centers as radiation attenuator and organic linkers as photo-responsive sensor. Interestingly, dual-module photochromic transitions upon multiple external stimuli including UV, β-ray, and γ-ray are integrated into this single material. The striking color change, and more significantly, the visible color transition of luminescence in response to accumulating radiation dose allow an on-site quantitative platform for naked-eye detection of ionization radiations over a broad range (1–80 kGy). Single crystal X-ray diffraction and density functional theory calculations reveal that the dual-module photochromism can be attributed to the π(TPC) → π*(TPC) intermolecular charge transfer driven by enhanced π-π stacking interaction between the adjacent TPC moieties upon irradiation.

Isoreticular expansion of Th-MOFs via modulated synthesis yielded seven hierarchical complexes with superior quality single crystals, record high void space and BET surface area among Th materials, and exceptional iodine adsorption capacities.

Effective capture of radioactiveiodine is of paramount importance for the safe and long-term storage of fission products in the nuclear fuel cycle. Herein, as eries of functionalized Th-UiO-66 MOFs wase mployed as a model to investigate the effects of substituents on iodine adsorption in both solution and vapor states. Sorption studies revealed that the electro-donating amino group exhibits the most positive role on increasing the removal rate of iodine from cyclohexane and the uptake capacity of iodine vapor.P articularly,t he disubstituted Th-UiO-66-(NH 2) 2 can effectively remove 91.9 %o fi odine (300 mg L À1) from cyclohexane and capture 969 mg g À1 iodine vapor, significantly highert han 59.6 %a nd 334 mg g À1 of untagged Th-UiO-66,r espectively.I na ddition, the substituent effect on the radiolytic stability of MOFs was for the first time investigated, leadingt ot he unearthing of one of the most radioresistant MOFs Th-UiO-66-NH 2 reportedt od ate.

Developing materials that possess colorimetric responses to external stimuli is a promising strategy for addressing the current challenges in radiation dosimetry. Currently, colorimetric ionizing-radiation-responsive materials remain underexplored, and those with multistimuli response are rare. Herein, the integration of thorium cation and photoresponsive terpyridine carboxylate ligand gives rise to a thorium nanocluster, Th-101, which displays the second case of fluorochromic response and unprecedented piezochromic behavior among all actinide materials. The emission color of Th-101 exhibits a gradual transition from blue to cyan to green upon irradiation with accumulated dose, which renders colorimetric dosimetry of ionizing radiation based on a red−green−blue (RGB) concept. Further fabricating Th-101 into a custom-built optoelectronic device allows for on-site quantification of radiation dose with merits of ease of operation, rapid readout, and cost-effectiveness.

A simple synthetic approach with [HCOOH]/[Th(iv)] and water controls the yield of six thorium formates with unexpected structural complexity.

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This perspective highlights the recent advances in the structural and practical aspects of thorium-based metal-organic frameworks (Th-MOFs) and molecular clusters. Thorium, as an underexplored actinide, features surprisingly rich coordination geometries...

The rational design and synthesis of metal−organic frameworks with wellcontrolled interpenetration have been active research areas of inquiry, particularly for porosityrelated applications. Herein, we extend the use of the ligand steric modulation strategy to initiate the first study of the interpenetration control of thorium-based MOFs. The approximate "hardness" of the Th 4+ cation, which was conjugated with aromatic substitutions and delicately modified synthetic conditions, allows for the crystallization of single crystals of seven new Th-MOFs with five distinct topologies. Solvothermal reactions of Th(NO 3 ) 4 with the triphenyl H 2 TPDC ligand under variable conditions exclusively gave rise to an interpenetrated Th-MOF with a hex topology, namely Th-SINAP-16. Modifications of the ligand sterics with two pendant methyl groups to 2′,5′-Me 2 TPDC 2− and 2,2″-Me 2 TPDC 2− afforded two noninterpenetrated UiO-68-type Th-MOFs (Th-SINAP-17 and Th-SINAP-20, respectively) with record-high pore volumes (74.8% and 75.3%, respectively) among all the thorium MOFs. Moreover, another four Th-MOFs Th-SINAP-n (n = 18, 19, 21, and 22) with three different topologies were obtained by a simple synthetic modulation. Notably, Th-SINAP-16 and Th-SINAP-21 represent the second rare examples of interpenetrated Th-MOFs reported to date. These findings revealed the unprecedented structural complexity and synthetic accessibility of Th-MOFs among all tetravalent metal containing MOFs. Such features make Th-MOFs as an ideal platform to elucidate the structure−property relationship for various applications, e.g. iodine adsorption.