ABSTRACT
Bis(bidentate) and bis(tridentate) Co(III) complexes of N-(2-hydroxyethyl)ethane-1,2-diamine (heen), 2-[(2-aminoethyl)amino]ethan-1-olate (heen-H), or N-(2-chloroethyl)ethane-1,2-diamine (ceen) ligands have been synthesised, and a range of reaction conditions established for their syntheses by different routes. They can all be ultimately derived from (OC-6-12')-[Co(heen)2(NO2)2]NO3 and provide access to the trans amine trans chloride nitrogen mustard complex, (OC-6-12')-[Co(ceen)2(Cl)2]Cl. Although complex isomeric mixtures were obtained from the reaction of (OC-6-12')-[Co(heen)2(NO2)2]NO3 under different reaction conditions, ultimately, the trans amine trans chlorido configuration around the Co(III) metal centre of the (OC-6-12')-[Co(ceen)2(Cl)2]Cl complex was favoured.
ABSTRACT
The properties of adamantane render it an attractive building block towards the synthesis of robust frameworks. This work describes the synthesis of the L-shaped 1,3-bis(3'-carboxypyridine)adamantane (L1) ligand and the corresponding Li(i), Zn(ii) and Cu(ii) frameworks. Three topologically analogous Li(i) frameworks LiMOF12, LiMOF30 and LiMOF50 are reported, with calculated solvent accessible void volumes of 46, 43 and 36%, respectively. The reaction between the carboxylate groups of L1 and the Li(i) cations resulted in the formation of Li-carboxylate rods. The Li-carboxylate rods contributed to the formation of a double-walled MOF with large, open one dimensional channels. The synergistic effect of the double wall, lithium-carboxylate rods and the adamantane core itself, resulted in the formation of a robust network stable up to temperatures of 300-350 °C and a minimum of three months stability in air. Furthermore, complexation of L1 with Cu(BF4)2·H2O and Zn(CF3SO3)2 provided a 2D â 3D interpenetrated network containing a classic dimeric copper paddle-wheel SBU, and an infinite 1D chain which extended into a 3D structure facilitated by hydrogen-bonding interactions, respectively.
