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Exploiting Synthetic Conditions to Promote Structural Diversity within the Scandium(III)/Pyrimidine-4,6-dicarboxylate System

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journal contribution
posted on 06.05.2015, 00:00 by Javier Cepeda, Sonia Pérez-Yáñez, Garikoitz Beobide, Oscar Castillo, Antonio Luque, Paul A. Wright, Scott Sneddon, Sharon E. Ashbrook
An exhaustive study of the factors governing the hydro- and solvothermal reaction of ScCl3 with pyrimidine-4,6-dicarboxylic acid (H2pmdc) has led to five Sc­(III)-organic architectures, namely {[Sc­(μ-pmdc)­(μ-ox)0.5(H2O)2]·3H2O}n (1), {[Sc­(μ-pmdc)­(μ-OH)­(H2O)]·H2O}n (2), {(NH4)­[Sc­(μ-ox)2]·2H2O}n (3), {(tma)2[ScK­(μ-form)6]}n (4), and [Sc2(pmdc)­(OH)3Cl]·DMF·2H2O (5) (where ox = oxalate, tma = tetramethylammonium, form = formate, DMF = dimethylformamide). In this system, the pmdc anion has proven to be particularly sensitive to changes in the synthetic conditions in the presence of Sc­(III), generating in situ byproducts that are incorporated into the final compounds. In fact, oxalate anions join the Sc-pmdc arrays into 2D sheets in 1 whereas ammonium ions fill the channels of the open 3D scandium oxalate architecture of 3. Making the reagent mixture a bit more basic prevents such decomposition and allows hydroxides to replace oxalate as ligands for the Sc, thus modifying the topology of layers in 2. Formate ions coming from the hydrolysis of DMF prevent the coordination of pmdc and give rise to the framework of 4. Structure 5 is an as yet unknown scandium pyrimidine-4,6-dicarboxylate framework which displays permanent porosity. CO2 adsorption isotherms on 5 reveal an uptake of 3 mmol g–1 and strong adsorbate···framework interactions. 45Sc MAS NMR has afforded additional information on the metal environments, providing further characterization of compound 5.