From Specific γ-CD/[Nb6 Cl12 (H2 O)6 ]2+ Recognition to Biological Activity Tuning.

Specific molecular recognition of γ-cyclodextrin (γ-CD) by the cationic hexanuclear niobium [Nb6 Cl12 (H2 O)6 ]2+ cluster complex in aqueous solutions results in a 1:1 supramolecular assembly {[Nb6 Cl12 (H2 O)6 ]@γ-CD}2+ . NMR spectroscopy, isothermal titration calorimetry (ITC), and ESI-MS were used to study the interaction between the inorganic cluster and the organic macrocycle. Such molecular association affects the biological activity of [Nb6 Cl12 (H2 O)6 ]2+ , decreasing its cytotoxicity despite enhanced cellular uptake. The 1:1 stoichiometry is maintained in solution over a large window of the reagents' ratio, but crystallization by slow evaporation produces a 1:2 host-guest complex [Nb6 Cl12 (H2 O)6 @(γ-CD)2 ]Cl2 ⋅20 H2 O featuring the cluster encapsulated between two molecules of γ-CD. The 1:2 complex was characterized by XRD, elemental analysis, IR spectroscopy, and thermogravimetric analysis (TGA). Quantum chemical calculations were performed to model host-guest interaction.

Lanthanide contraction effect and white-emitting luminescence in a series of metal-organic frameworks based on 2,5-pyrazinedicarboxylic acid.

A series of lanthanide and yttrium MOFs of two structural types [M2(H2O)2(nmp)2(pzc)3] (1M) and [M2(H2O)4(pzc)3]·NMP·5H2O (2M) (where M - lanthanide or yttrium cation, nmp - N-methyl-2-pyrrolidone, pzc2- - 2,5-pyrazinedicarboxylate) was synthesized and characterized by single crystal and powder X-ray diffraction crystallography, TG, elemental analyses and IR-spectroscopy. The effect of lanthanide contraction has led to the fact that lanthanides at the beginning of the series (from lanthanum to gadolinium) have a structure different from the structure of lanthanides at the end of the series and yttrium (from terbium and beyond). According to PXRD patterns of the obtained samples mixed metal materials could be obtained not only as crystalline mixtures of two structure types but also as crystalline products of single structure type. Varying the ratio of lanthanides in the initial reaction mixture allowed us to obtain a wide color range of luminescence, including several near-white-light emitting samples.