Unexpected structural complexity of thorium coordination polymers and polyoxo cluster built from simple formate ligands

Abstract

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

Interpenetration Control in Thorium Metal–Organic Frameworks: Structural Complexity toward Iodine Adsorption

“…We have recently undertaken studies of the modulated synthesis of thorium-based MOFs for radioactive iodine adsorption because of the propensity of these materials to exhibit tunable pore sizes, void spaces, and surface areas for guest–host chemistry. − Radioactive iodine represents one of the most critical fission products in nuclear waste disposal due to its high volatility, fast diffusion, and active involvement in metabolism. , Since both 129 I and 131 I have much shorter half-lives (1.57 × 10 7 y and 8.02 d, respectively) than that of 232 Th ( t 1/2 = 1.405 × 10 10 y), the slightly radioactive nature of thorium can be virtually neglected for iodine remediation. , A number of thorium-bearing MOFs featuring iodine absorption are known, including Ni 3 Th 6 ­(O) 4 (OH) 4 ­(IN) 12 )­(H 2 O) 12 ]·(OH) 6 ·5DMF·2H 2 O, Th 6 O 4 ­(OH) 4 (H 2 O) 6 ­(H 2 TTHA) 2 ­(HCO 2 ) 4 , Th 6 O 4 ­(OH) 4 ­(H 2 O) 6 ­(TATAB) 2 ­(HCO 2 ) 6 , and our recently reported Th-SINAP - n ( n = 7–15) and its derivatives. ,,− Different approaches, such as increasing the pore volume and surface area, tuning the shape and aperture of the pores, introducing electron-rich functional groups, etc., have been utilized to improve the adsorption performance by using Th-MOFs as a platform.…”

“…Each Th 6 (μ 3 -OH) 4 (μ 3 -O) 4 (DMF) 4 (H 2 O) 2 metal node connects to ten neighboring SBUs via ten TPDC linkers, leading to a 10connected uninodal 3D porous framework (Figure 4c). Furthermore, two independent networks interpenetrate each other, thus furnishing a twofold-interpenetrated porous framework that can be best assigned as a bct net with the point symbol of 3 12 .4 28 .5 5 (Figure 4d and e). Th-SINAP-21 shows the lowest solvent accessible void (36.6%) among all the Th-MOFs reported herein.…”

An Azobenzene-Modified Photoresponsive Thorium–Organic Framework: Monitoring and Quantitative Analysis of Reversible trans–cis Photoisomerization

“…Its coordination number can range from 5 to 12 or more, making it easier to produce interesting and stable topological structures. Th IV is considered an ideal surrogate for studying the much more radiotoxic Pu IV owning to its exclusive tetravalent state in nature and similarities in coordination behavior with Pu. , Moreover, because of the particularity of the intrinsic radioactivity and 5f orbitals for the actinide center, actinide organic frameworks often have special properties, such as self-photoluminescence, radionuclide remediation, − X-ray scintillators, and structural memory . Most importantly, as demonstrated above, the larger pores in thorium–organic frameworks help to further reduce the cumbersome steric hindrance around azobenzene, thus facilitating its enhanced photoresponse.…”

SAXS study of the formation and structure of polynuclear thorium(IV) colloids and thorium dioxide nanoparticles

“…Thorium(IV) is an analog for studying the tetravalent state of the more radiologically and chemically toxic Pu(IV) because of their similar coordination chemistry (Li et al, 2020) and ionic radii which are 0.108 nm and 0.096 nm for thorium and plutonium, respectively. Despite minor differences in their properties, a tenfold coordination for Th 4 and a slightly larger ionic radius, recent light scattering measurements of thorium polymers and colloids formed in the acidic solutions tend to highlight the similarities between the hydrolytic reactions of Th(IV) and Pu(IV) (Priyadarshini et al, 2016).…”