화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.124, No.38, 7678-7684, 2020
Lanthanide Contraction in Lanthanide Organic Frameworks: A Theoretical and Experimental Study
In this work, the lanthanide (Ln) contraction phenomenon has been analyzed for three-dimensional structures in the solid state. We chose to study an isostructural series of lanthanide organic frameworks (LOFs) of formula [Ln(2)(C4H4O4)(3)(H2O)(2)](n)center dot H2O and 14 crystallographic structures (except promethium complex). The analysis of Ln contraction was made by analyzing the sum of all Ln-O bond lengths and the sum of all O-O distances, for the oxygen atoms of the coordination polyhedra, calculated with different semiempirical quantum mechanical models. The Sigma(Ln-O) and Sigma(O-O) for this LOF can be fit to a second-order polynomial. Based on the crystallographic structures, it is concluded that the phenomenon of Ln contraction is observed. Our results also suggest that the semiempirical Sparkle/PM3 and Sparkle/RM1 models reproduce the Ln contraction phenomenon well, and similar fits were obtained for Sigma(Ln-O) and Sigma(O-O) bond lengths.