International audienceHerein, we report on a three-component supra molecular hybrid system built from specific recognition processes involving a Dawson-type polyoxometalate (POM) ,P2W18O62](6-), a cationic electron-rich cluster [Ta6Br12(H2O)(6)](2+), and gamma-cyclodextrin (gamma-CD). Such materials have been investigated using a bottom-up approach by studying the specific interactions between gamma-CD and both types of inorganic units. Their ability to interact has been investigated in the solid state by single-crystal X-ray diffraction (XRD) and in solution using multinuclear NMR methods (including DOSY, EXSY, and COSY), electrospray ionization mass and UV-vis spectroscopies, electrochemistry, and isothermal titration calorimetry experiments. Single-crystal XRD analysis reveals that POM:gamma-CD constitutes a highly versatile system which gives aggregates with 1:1, 1:2, and 1:3 stoichiometry. Surprisingly, these arrangements exhibit a common feature wherein the gamma-CD moiety interacts with the Dawson-type POMs through its primary face. We present also the first structural model involving an octahedral-type metallic cluster with gamma-CD. XRD study reveals that the cationic [Ta6Br12(H2O)(6)](2+) ion is closely embedded within two gamma-CD units to give a supramolecular ditopic cation, suitable to be used as a linker within extended structure. Solution study demonstrates clearly that pre-associations exist in solution, for which binding constants and thermodynamic parameters have been determined, giving preliminary arguments about the chaotropic nature of the inorganic ions. Finally, both building blocks, i.e., the ditopic supramolecular cation {[Ta6Br12(H2O)(6)]@2CD}(2+) and the Dawson-type anion, react together to give a three-component, well-ordered hybrid material derived either as a supramolecular hydrogel or single crystals. The solid-state structure shows an unprecedented helicoidal tubular chain resulting from the periodic alternation of POM and supramolecular cation, featuring short hydrogen-bonding contacts between the electron-poor POM and electron-rich cluster. The 1D tubular ionic polymer observed in the single crystals should make it possible to understand the long-range ordering observed within the hydrogel hybrid material. The supramolecular chemical complementarities between the gamma-CD-based ditopic cation and POM open a wide scope for the design of hybrid materials that accumulate synergistic functionalities

The reactions between the tetra-n-butylammonium salt of [{Mo6I8}I6](2-) and silver carboxylates RCOOAg (R = CH3 (1), C(CH3)3 (2), α-C4H3O (3), C6H5 (4), α-C10H7 (5), or C2F5 (6)) in CH2Cl2 afforded new carboxylate complexes [{Mo6I8}(RCOO)6](2-). The complexes were characterized by X-ray single-crystal diffraction and elemental analysis, cyclic/differential pulse voltammetry, and IR, NMR, and UV-visible spectroscopies. The emission properties of the complexes 1-6, and those of the earlier reported complexes with R = CF3 (7) and n-C3F7 (8), were studied both in acetonitrile solution and in the solid state. In deaerated CH3CN at 298 K, all of the complexes 1-8 exhibit intense and long-lived emission with the quantum yield and lifetime being 0.48-0.73 and 283-359 μs, respectively. The oxidation (Eox)/reduction (Ered) potentials of the complexes correlate linearly with the pKa value of the terminal carboxylate ligands L = RCOO (pKa(L)). Reflecting the pKa(L) dependences of Eox/Ered, the emission energy (νem) of the complexes was also shown to correlate with pKa(L). The present study successfully demonstrates synthetic tuning of the redox, spectroscopic, and photophysical characteristics of a {Mo6I8}(4+)-based cluster complex with pKa(L).

In this communication, we report on a noteworthy hybrid supramolecular assembly built from three functional components hierarchically organized through noncovalent interactions. The one-pot synthesis procedure leads to the formation of large Mo-blue ring-shaped anion {Mo}, which contains the supramolecular adduct based on the symmetric encapsulation of the Dawson-type [PWO] anion by two γ-cyclodextrin units. Such a nanoscopic onion-like structure, noted [PWO]@2γ-CD@{Mo} has been characterized by single-crystal X-ray diffraction, thus demonstrating the capability of the giant inorganic torus to develop relevant supramolecular chemistry, probing the strong affinity of the inner and outer faces of the γ-CD for the polyoxometalate surfaces. Furthermore, interactions and behavior in solution have been studied by multinuclear NMR spectroscopy, which supports specific interactions between γ-CD and POM units. Finally, the formation of this three-component hybrid assembly from one-pot procedure, in water and using nearly stoichiometric conditions, is discussed in terms of the driving forces orchestrating this highly efficient multilevel recognition process.