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 - 2015/6
Y1 - 2015/6
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 °C and the weight loss at ∼300 °C is due to the loss of water molecules in the solvent accessible voids in the crystal lattice.
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 °C and the weight loss at ∼300 °C is due to the loss of water molecules in the solvent accessible voids in the crystal lattice.
KW - Thorium
KW - Polycarboxylate
KW - Frameworks
KW - X-ray diffraction
UR - http://www.scopus.com/inward/record.url?scp=84940381690&partnerID=8YFLogxK
U2 - 10.1007/s10847-015-0506-y
DO - 10.1007/s10847-015-0506-y
M3 - Article
AN - SCOPUS:84940381690
VL - 82
SP - 163
EP - 172
JO - Journal of Inclusion Phenomena and Macrocyclic Chemistry
JF - Journal of Inclusion Phenomena and Macrocyclic Chemistry
SN - 1388-3127
IS - 1-2
ER -