Structural re-arrangement in two hexanuclear CuII complexes: from a spin frustrated trigonal prism to a strongly coupled antiferromagnetic soluble ring complex with a porous tubular structure
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The addition of water to a chloroform solution of the Cu6 trigonal prism complex [Cu6(U6F)(U2OH)(U3OCH3)2(U2OCH3)2(3,5-Me2pz)6] (1) (3,5-Me2pz- = 3,5-dimethylpyrazolate) results in the formation of the Cu6 planar hexagonal ring complex [Cu6(U2OH)6(3,5-Me2pz)6]CH3CN CHCl3 (2). A simple mechanism for this structural re-arrangement is proposed, in which 2 can be viewed as a hydrolysis product of 1. This process is clearly noticeable in the magnetic properties, which change from spin frustrated with a weak antiferromagnetic coupling in 1, to strongly antiferromagnetic in 2. Interestingly, the hexagonal ring complex 2 self-assembles in the solid state to form a porous hexagonal tubular structure containing guest solvent molecules that can be removed and CO2-exchanged without loss of crystallinity.
Artículo de publicación ISI
We acknowledge the European Union (Advanced ERC grant SPINMOL), the Spanish MINECO (projects Consolider-Ingenio in Molecular Nanoscience, CTQ2011-26507 and MAT2011- 22785) and the Generalidad Valenciana (Prometeo and ISICNano Programs) for nancial support. The work in Chile has been supported by the Financiamiento Basal Program FB0807. WCM thanks CONICYT for Doctoral Scholarships (21080445 and AT24100006), and Becas Chile. The authors also thank Powered@NLHPC. This research was partially supported by the Supercomputing Infrastructure of the National Laboratory for High Performance Computing, NLHPC (ECM-02), Centre for Mathematical Modeling (CMM), Universidad de Chile.
DOI: DOI: 10.1039/c3sc52628c
Quote ItemChem. Sci., 2014, 5, 324