Twelve novel coordination polymers and supramolecular architectures have been obtained using the bent ditopic ligand 4,4'-diaminodiphenylmethane (dadpm) and different metal salts ( chlorides and nitrates), and their structures have been elucidated by single crystal X-ray analysis. The new products include some examples of simple zigzag chains, as in [MCl2(dadpm)] [M = Co ( 1); M = Cd ( 2)] and [Ag(NO3)(dadpm)] ( 3). The chains are connected via weaker interactions (H-bonds or contacts with the anions) to give 2-D layers. In [Ni(H2O)(2)(dadpm)(2)] Cl-2 ( 4) the polymeric 1-D chains consist of parallel ribbons of rings with the non-coordinated chloride anions generating a 3-D architecture via NH center dot center dot center dot Cl bonds. Noteworthy, compound 5a, [Ni(H2O)(2)Cl-2(dadpm)(2)], has an identical composition but a different structure, thus representing a novel case of supramolecular isomerism: it contains mononuclear octahedral complexes, with two trans coordinated H2O molecules, two trans Cl anions and two trans monodentate dadpm ligands. The dangling ends of the dadpm ligands, however, form H-bonds with the H2O molecules coordinated on adjacent complexes, thus giving rise to double-stranded chains resembling the ribbons of rings present in 4. Compound 5b, [Mn(H2O)(2)Cl-2(dadpm)(2)], is isomorphous with 5a and also compound 6, [Ni(H2O)(2)(NO3)(2)(dadpm)(2)], shows a similar structure. Compounds [ MCl2( dadpm)] [ M 5 Cd ( 7); M 5 Mn ( 8)] are isostructural, but not isomorphous, and contain single 3-D networks with the ths (ThSi2) topology. In compound 9, [CdCl2(dadpm)], complex 2-D layers of (6,3) topology are observed. The structure of [Cd3Cl6(dadpm)(2)] (10) is comprised of complex Cd/Cl chains inter-connected by double bridging dadpm ligands to give a 3-D network with the cds (CdSO4) topology (or, alternatively, the cds-a augmented topology). In [Ag(dadpm)(3)](NO3) ( 11) the Ag centres are octahedrally coordinated by six bridging dadpm ligands, resulting in a 3-D network with the pcu (alpha-Po) topology. It is worth mentioning that three compounds (2, 7 and 9, of composition [CdCl2(dadpm)]) show a remarkable case of supramolecular isomerism.
New metal-organic frameworks and supramolecular arrays assembled with the bent ditopic ligand 4,4-diaminodiphenylmethane. / L. Carlucci, G. Ciani, D.M. Proserpio, F. Porta. - In: CRYSTENGCOMM. - ISSN 1466-8033. - 8:9(2006), pp. 696-706.
New metal-organic frameworks and supramolecular arrays assembled with the bent ditopic ligand 4,4-diaminodiphenylmethane.
L. Carlucci;G. Ciani;D.M. Proserpio;F. Porta
2006
Abstract
Twelve novel coordination polymers and supramolecular architectures have been obtained using the bent ditopic ligand 4,4'-diaminodiphenylmethane (dadpm) and different metal salts ( chlorides and nitrates), and their structures have been elucidated by single crystal X-ray analysis. The new products include some examples of simple zigzag chains, as in [MCl2(dadpm)] [M = Co ( 1); M = Cd ( 2)] and [Ag(NO3)(dadpm)] ( 3). The chains are connected via weaker interactions (H-bonds or contacts with the anions) to give 2-D layers. In [Ni(H2O)(2)(dadpm)(2)] Cl-2 ( 4) the polymeric 1-D chains consist of parallel ribbons of rings with the non-coordinated chloride anions generating a 3-D architecture via NH center dot center dot center dot Cl bonds. Noteworthy, compound 5a, [Ni(H2O)(2)Cl-2(dadpm)(2)], has an identical composition but a different structure, thus representing a novel case of supramolecular isomerism: it contains mononuclear octahedral complexes, with two trans coordinated H2O molecules, two trans Cl anions and two trans monodentate dadpm ligands. The dangling ends of the dadpm ligands, however, form H-bonds with the H2O molecules coordinated on adjacent complexes, thus giving rise to double-stranded chains resembling the ribbons of rings present in 4. Compound 5b, [Mn(H2O)(2)Cl-2(dadpm)(2)], is isomorphous with 5a and also compound 6, [Ni(H2O)(2)(NO3)(2)(dadpm)(2)], shows a similar structure. Compounds [ MCl2( dadpm)] [ M 5 Cd ( 7); M 5 Mn ( 8)] are isostructural, but not isomorphous, and contain single 3-D networks with the ths (ThSi2) topology. In compound 9, [CdCl2(dadpm)], complex 2-D layers of (6,3) topology are observed. The structure of [Cd3Cl6(dadpm)(2)] (10) is comprised of complex Cd/Cl chains inter-connected by double bridging dadpm ligands to give a 3-D network with the cds (CdSO4) topology (or, alternatively, the cds-a augmented topology). In [Ag(dadpm)(3)](NO3) ( 11) the Ag centres are octahedrally coordinated by six bridging dadpm ligands, resulting in a 3-D network with the pcu (alpha-Po) topology. It is worth mentioning that three compounds (2, 7 and 9, of composition [CdCl2(dadpm)]) show a remarkable case of supramolecular isomerism.Pubblicazioni consigliate
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