A three-dimensional homochiral metal–organic framework constructed from manganese(II) withS-carboxymethyl-N-(p-tosyl)-L-cysteine and 4,4′-bipyridine

Abstract

In the chiral polymeric title compound, poly[aqua(4,4'-bipyridine)[mu(3)-S-carboxylatomethyl-N-(p-tosyl)-L-cysteinato]manganese(II)], [Mn(C(12)H(13)NO(6)S(2))(C(10)H(8)N(2))(H(2)O)](n), the Mn(II) ion is coordinated in a distorted octahedral geometry by one water molecule, three carboxylate O atoms from three S-carboxyatomethyl-N-(p-tosyl)-L-cysteinate (Ts-cmc) ligands and two N atoms from two 4,4'-bipyridine molecules. Each Ts-cmc ligand behaves as a chiral mu(3)-linker connecting three Mn(II) ions. The two-dimensional frameworks thus formed are further connected by 4,4'-bipyridine ligands into a three-dimensional homochiral metal-organic framework. This is a rare case of a homochiral metal-organic framework with a flexible chiral ligand as linker, and this result demonstrates the important role of noncovalent interactions in stabilizing such assemblies.

Noncentrosymmetric and Homochiral Metal−Organic Frameworks of (S)-2-(1H-Imidazole1-yl) Propionic Acid

“…Generally, noncentrosymmetric solids based on infinite networks can be rationally designed by taking advantage of well-defined metal coordination geometries in combination with carefully chosen bridging ligands . Several approaches toward the achievement of noncentrosymmetric crystalline solids with promising NLO properties have appeared in recent years, − of which the employment of chiral organic linkers to generate noncentrosymmetric or chiral metal−organic frameworks (MOFs) is the most convenient and effective strategy. The achiral ligand of 2-(1 H -imidazole-1-yl) acetic acid (Hima) has been recently reported to form one- and two-dimensional (1D, 2D) centrosymmetric MOFs of [M(ima) n ] ∞ , (M = Ag (I), n = 1; M = Mn(II), Cu(II), Ni(II), and Cd(II), n = 2). , However, we noticed that its structure-similar chiral compound of ( S )-2-(1 H -imidazole1-yl) propionic acid (H - ( S ) - imp) (Scheme ) has been, so far, merely prepared as an intermediate compound for chiral ionic liquids .…”