title: Centrosymmetric and chiral porous thorium organic frameworks exhibiting uncommon thorium coordination environments.
abstract: The solvothermal reaction of thorium nitrate and tris-(4-carboxylphenyl)phosphine oxide in DMF affords a centrosymmetric porous thorium organic framework compound [Th(TPO)(OH)(H2O)]·8H2O (1). In contrast, the ionothermal reaction of the same reagents in the ionic liquid 1-butyl-2,3-dimethylimidazolium chloride results in the formation of a rare example of a chiral and porous thorium organic framework compound, [C9H17N2][Th(TPO)Cl2]·18H2O (2), which is derived solely from achiral starting materials. The geometries of the Th(iv) centers in compounds 1 and 2 are both atypical for low valent actinides, which can be best described as a ten-coordinate spherical sphenocorona and an irregular muffin, respectively. A large cavity of 17.5 Å (max. face to face) × 8 Å (min. face to face) with a BET surface area of 623 m(2) g(-1) in compound 2 is observed. The poor stability indicated by thermal gravimetric analysis and the water-resistance test for compound 2 may be due to the unique anisotropic coordination geometry for thorium. Temperature-dependent luminescence studies for both compounds indicate that the trends in the intensity vary as the Th-Th distance and the coordination environments of Th(iv) centers change.
authors.affiliation: State Key Laboratory Breeding Base of Nuclear Resources and Environment, East China Institute of Technology, Nanchang, 330013, China. walton_liu@163.com.
authors.forename: Yuxiang
authors.initials: Y
authors.lastname: Li
authors.forename: Zhehui
authors.initials: Z
authors.lastname: Weng
authors.forename: Yanlong
authors.initials: Y
authors.lastname: Wang
authors.forename: Lanhua
authors.initials: L
authors.lastname: Chen
authors.forename: Daopeng
authors.initials: D
authors.lastname: Sheng
authors.forename: Yunhai
authors.initials: Y
authors.lastname: Liu
authors.forename: Juan
authors.initials: J
authors.lastname: Diwu
authors.forename: Zhifang
authors.initials: Z
authors.lastname: Chai
authors.forename: Thomas E
authors.initials: TE
authors.lastname: Albrecht-Schmitt
authors.forename: Shuao
authors.initials: S
authors.lastname: Wang