We report the two-step synthesis of a chiral rod-like metal-organic framework (MOF). The chemical approach consists on the use of a previously prepared oxamato-based homochiral hexanuclear wheel, the ligand being a derivative of the natural amino acid Lalanine, with formula (Me4N)6{CuII 6[(S)-alama])6}10H2O (1) [where (S)-alama¼(S)-N-(ethyl oxoacetate)alanine]. The anionic hexacopper(II) wheels, stabilized by the presence of templating tetramethylammonium counter-cations, disassemble in the presence of cationic square-planar [Ni(cyclam)]2þ complexes to yield, after a supramolecular reorganization process that involves axial coordination of the [Ni(cyclam)]2þ cations through the free carbonyl groups of the copper(II) moieties, a neutral chiral rod-like, three-dimensional (3D) MOF with formula [Ni(cyclam)][Cu(S)- alama]216H2O (2). The resulting MOF constitutes one of the few examples where such a high-nuclearity metal complex is used as precursor for the construction of rod-like MOFs.

Synthesis of a chiral rod-like metal–organic framework from a preformed amino acid-based hexanuclear wheel

Armentano, D.;
2019

Abstract

We report the two-step synthesis of a chiral rod-like metal-organic framework (MOF). The chemical approach consists on the use of a previously prepared oxamato-based homochiral hexanuclear wheel, the ligand being a derivative of the natural amino acid Lalanine, with formula (Me4N)6{CuII 6[(S)-alama])6}10H2O (1) [where (S)-alama¼(S)-N-(ethyl oxoacetate)alanine]. The anionic hexacopper(II) wheels, stabilized by the presence of templating tetramethylammonium counter-cations, disassemble in the presence of cationic square-planar [Ni(cyclam)]2þ complexes to yield, after a supramolecular reorganization process that involves axial coordination of the [Ni(cyclam)]2þ cations through the free carbonyl groups of the copper(II) moieties, a neutral chiral rod-like, three-dimensional (3D) MOF with formula [Ni(cyclam)][Cu(S)- alama]216H2O (2). The resulting MOF constitutes one of the few examples where such a high-nuclearity metal complex is used as precursor for the construction of rod-like MOFs.
Metal–organic framework; complex-as-ligand; copper(II); chirality
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/20.500.11770/289232
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