TY - JOUR
T1 - Thorium(IV) organic frameworks with aromatic polycarboxylate ligands
AU - Zhang, Yingjie
AU - Kadi, Fatima
AU - Karatchevtseva, Inna
AU - Price, Jason R.
AU - Murphy, Timothy
AU - Wuhrer, Richard
AU - Li, Feng
AU - Lumpkin, Gregory R.
PY - 2015
Y1 - 2015
N2 - Contrary to the fairly well established structural chemistry of uranium(VI) with aromatic polycarboxylate ligands, the knowledge on thorium(Th) structural chemistry with this family of ligands is very limited. In this paper, we report the synthesis, spectroscopic and thermal studies, and crystal structures of three Th organic frameworks with 1,2,4,5-benzenetetracarboxylate (btca) or 1,4- benzenedicarboxylate (bdc). Both [Th(btca)(DMF)2(H2O)] (1) and [Th(bdc)2(DMF)2] (2) (DMF = dimethylformamide) have two dimensional (2D) layered structures constructed with 9- (1) or 10- (2) fold coordinated Th polyhedrons and µ4-btca (1) or µ2-bdc (2) ligands, respectively, with two coordinated DMF molecules in cis- (1) or trans- (2) positions on each Th atom. The third phase, [Th(bdc)2] (3), has a 3D pillared framework built with eightfold coordinated Th polyhedrons and µ4-bdc ligands. Their vibrational modes have been investigated and correlated to the structures. VT-PXRD confirmed that 3 is thermally robust to 500 ᵒC and the weight loss at 300 ᵒC is due to the loss of water molecules in the solvent accessible voids in the crystal lattice. Graphical Abstract Thorium(IV) organic frameworks (TOC): Three new thorium organic frameworks with aromatic polycarboxylate ligands have been synthesized and characterized. 2D layered structures are favored at room temperature and a thermal robust, 3D thorium organic framework has been made under hydrothermal conditions. Their vibrational modes and thermal stabilities have been further investigated.
AB - Contrary to the fairly well established structural chemistry of uranium(VI) with aromatic polycarboxylate ligands, the knowledge on thorium(Th) structural chemistry with this family of ligands is very limited. In this paper, we report the synthesis, spectroscopic and thermal studies, and crystal structures of three Th organic frameworks with 1,2,4,5-benzenetetracarboxylate (btca) or 1,4- benzenedicarboxylate (bdc). Both [Th(btca)(DMF)2(H2O)] (1) and [Th(bdc)2(DMF)2] (2) (DMF = dimethylformamide) have two dimensional (2D) layered structures constructed with 9- (1) or 10- (2) fold coordinated Th polyhedrons and µ4-btca (1) or µ2-bdc (2) ligands, respectively, with two coordinated DMF molecules in cis- (1) or trans- (2) positions on each Th atom. The third phase, [Th(bdc)2] (3), has a 3D pillared framework built with eightfold coordinated Th polyhedrons and µ4-bdc ligands. Their vibrational modes have been investigated and correlated to the structures. VT-PXRD confirmed that 3 is thermally robust to 500 ᵒC and the weight loss at 300 ᵒC is due to the loss of water molecules in the solvent accessible voids in the crystal lattice. Graphical Abstract Thorium(IV) organic frameworks (TOC): Three new thorium organic frameworks with aromatic polycarboxylate ligands have been synthesized and characterized. 2D layered structures are favored at room temperature and a thermal robust, 3D thorium organic framework has been made under hydrothermal conditions. Their vibrational modes and thermal stabilities have been further investigated.
KW - frameworks
KW - ligands
KW - thorium
KW - x-ray diffraction
UR - http://handle.uws.edu.au:8081/1959.7/uws:29948
U2 - 10.1007/s10847-015-0506-y
DO - 10.1007/s10847-015-0506-y
M3 - Article
SN - 1388-3127
VL - 82
SP - 163
EP - 172
JO - Journal of Inclusion Phenomena and Macrocyclic Chemistry
JF - Journal of Inclusion Phenomena and Macrocyclic Chemistry
IS - 45323
ER -