Nathalie Kyritsakas-Gruber

Metallacrown ethers: synthesis and structural investigation of silver metallamacrocycles

The bis-monodentate ligands 1 and 2 based on the interconnection of two pyrazolyl units by CH 2 (CH 2 OCH 2 ) n CH 2 ( n =3 or 4) spacers, respectively, lead to the formation of either mono nuclear silver metallamacrocycle 10 in the case of 1 or binuclear silver metallamacrocycle 11 in the case of 2 . Both complexes have been characterised in the solid state by X-ray diffraction on single crystals.

Synthesis and Properties of Oligo[n]cruciforms: Nanosized Sterically Encumbered Tetraethynylphenyl-Homologated Fluorophores

A series of nanosized phenyleneethynylenes have been prepared which are sterically insulated from the surrounding environment by multiple functionalization with triisopropylsilyl (TIPS) substituents. The phenyleneethynylenes comprise oligo[n]cruciforms 1-4 (n = 3-5) and a dehydrotribenzo[12]annulene 5, the former of which possess para-acyclic and the latter ortho-cyclic electronic conjugation pathways. All compounds were characterized by (1)H and (13)C NMR, IR, and mass spectroscopic techniques. The X-ray crystal structure of 1 confirmed the sterically isolating properties of the TIPS substituents. A comparison of the physical properties of these electronically differing systems revealed that they were all luminescent upon UV irradiation displayed negligible aggregation in dilute solution and that particular members of the series studied were electrochemically active, undergoing facile reversible reductions. The phenyleneethynylenes also exhibited significantly enhanced thermal stability by virtue of the presence of the TIPS substituents. The properties of 1-5 suggest that they are promising building blocks for the construction of materials for novel molecular electronics applications.

Direct synthesis and structural characterisation of tri- and tetra-nuclear silver metallaknotanes by self-assembly approach

The combination of ligands based on two quinoline units acting as primary coordinating sites connected by tetra- or penta-ethyleneoxy fragments behaving as secondary interaction sites leads spontaneously in a one-pot reaction to the formation of tri- and terta-nuclear metalla-organic knots in the presence of silver cation.

Synthesis and Solid‐State Structural Analysis of Exotetradentate Ligands Based on Mesitylene‐Derived [1.1.1.1]Metacyclophane Fixed in a 1,3‐Alternate Conformation

A series of new tetradentate ligands based on the [1.1.1.1]metacyclophane backbone fixed in a 1,3-alternate conformation was achieved. For the strategy developed, the common synthon for the preparation of twelve ligands bearing four interaction sites occupying the apices of a pseudo-tetrahedron [H, SH, CN, SCH3, CO2H, CHO, PPh2, P(O)Ph2, NO2, NH2, pyridine, and para-methoxyphenyl] was the tetrabromo derivative 7. In addition to the classical characterisation methods applied to all reported ligands, compounds 7, 9, 12, and 13 were structurally studied in the solid state by single-crystal X-ray diffraction, which indeed confirmed their 1,3-alternate conformation.

Molecular tectonics: generation and structural studies on 1- and 2D coordination networks based on a meta-cyclophane in 1,3-alternate conformation bearing four pyrazolyl units and cobalt, zinc and copper cations.

The combination of a [1111] metacyclophane blocked in 1,3-alternate conformation and bearing four pyrazolyl coordinating units with MX(2) (M = Co, Zn and X = Cl or Br) leads to the formation of crystals formed by packing of 2D coordination networks. In the case of CuBr(2), the formation of a 1D network was observed. Structural studies by X-ray diffraction methods on single crystals were performed on all cases reported.

New manganese-scaffolded organic triple-deckers based on quinoxaline, pyrazine and pyrimidine cores

The thermolytic coupling of Ph(2)CN(2) and (t-Bu)(Ph)CN(2) with doubly cyclomanganated 2,5-diphenylpyrazine and 4,6-diphenylpyrimidine afforded substantial amounts of new triple decker compounds of either C(i) and C(2) symmetry respectively containing, in both series, two eta(3)-bonded Mn(CO)(3) fragments which intervene as scaffolds sustaining the helical non-conjugated triaryl backbone. The molecular structures of two pyrazine derivatives show a typical non-parallel stacking of the aromatic rings and the encapsulation of the central pyrazyl fragment with interplanar centroid-to-centroid distances of ca. 3.5 A. The stacking of the aromatics in the triple-decker pyrimidine derivatives has been assessed by (1)H NMR experiments at low temperature. All the triple-decker-type compounds are electroactive. Pyrimidine triple-deckers can reversibly be electrochemically reduced to the corresponding anions.

Molecular tectonics: design and structural analysis of 1-D and 2-D self-inclusion molecular networks in the crystalline state

Abstract The synthesis of the new symmetrical koiland 2 based on the double fusion of two p-ethylcalix〚4〛arene in cone conformation by two silicon atoms was achieved and its structure confirmed by X-ray diffraction on a single crystal. Koiland 2, a concave building block possessing two calix-type pre-organised cavities disposed in a divergent fashion as well as ethyl groups as potential connector moieties, affords either a discrete exo-binuclear inclusion complex in the solid state in the presence of p-xylene acting as a stopper or infinite 1-D or 2-D self-inclusion networks or koilates, mainly based on van der Waals interactions and resulting from the inclusion processes taking place between concave and convex moieties of consecutive koilands.