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donglijie银虫 (初入文坛)
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Crystal engineering based on metal-organic framework materials (MOFs) is a topic of large, growing interest of modern coordination chemistry.1As a matter of fact, these compounds possess unique open-framework structures and can have appli-cations in the storage of gases, as catalysts, and in separation and exchange reactions (zeolitic-like MOFs).2 Recently, new fascinating MOFs, having flexible networks, which can change their structures to respond to external stimuli, have been reported.3 Actually, most coordination polymers have been assembled through processes either not completely clarified or serendi-pitous. Therefore, it is a great challenge for the chemists in this field to design rational strategies for the synthesis of networks having determined compositions and structures. Unfortunately, evensmall variations of onlyoneof the several factors influencing the synthetic process (metal ion, ligand, solvent, temperature, pH, etc.) can dramatically change the framework structure. 4 We have shown in the last years that P,P0 -diphenyl-dipho-sphinate anions are useful ligands to bridge metal ions in poly-meric networks of different geometries (1D, 2D, 3D).5 As a matter of fact, we found that the two closely related H2pcp and H2pc2p acids (see Scheme 1) react with the Cu(acetate)2/4,40-bipy system, under the same reactionconditions, toassembleMOFsof different topology: namely, a 1D tubelike network, in the case ofH2pcp,5gand a metastable 3D cds one which spontaneously changes into a 2D grid, in the case of H2pc2p.5i Some peculiar properties of the latter networks are consistent with the ability of the ethylene chain to assume different conformations. To further investigate the influence of the skeleton connecting the diphosphinatemoieties to the structure of the resultingMOF, now we allowed the systemCu(acetate)2/4,4bipy to react, under the same usual conditions, with theP,Pdiphenylp-xylene dipho-sphinic acid, H2 p(xyl)p, synthesized by us.In this latter, the skeleton should be more rigid and the two phosphinic groups are quite far away; therefore, the p(xyl)p 2-anion ligand should be unable to chelate a single metal center |
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