Sylvie Ferlay

Molecular tectonics: generation of 2-D molecular networks by combination of coordination and hydrogen bonds

The combination of two organic tectons 1 and 2, based on a 1,4-phenylenediamine backbone functionalised with two pyridine units through amide junctions with HgCl2, leads to the formation of two types of 2-D networks, one of the purely metallo-organic type, based on only coordination bonds, and the other combining both coordination and hydrogen bonds.

Alkoxo-bridged copper(II) complexes as nodes in designing solid-state architectures. The interplay of coordinative and d10-d10 metal-metal interactions in sustaining supramolecular solid-state architectures

Four novel polymeric coordination networks have been obtained through self-assembly processes involving alkoxo-bridged copperII species as nodes, and anionic cyano-complexes as linkers: infinity2[{Cu2(pa)2}{M(CN)2}2](M=Ag, 1; Au, 2), (infinity)3[{Cu4(mea)4}{Au(CN)2}4.H2O]3, and (infinity)3[{Cu2(pa)2}{Ni(CN)4}](pa = deprotonated propanolamine; mea = deprotonated monoethanolamine). The supramolecular architectures of compounds 1, and 2 are sustained by argentophilic or strong aurophilic interactions. The solid-state architectures of 1 and 2, which are isomorphous, consist of infinite layers, constructed from binuclear alkoxo-bridged nodes and [M(CN)2]- spacers. The layers are stacked in an offset parallel mode, and are further interconnected through Ag...Ag or Au...Au contacts (1: Ag...Ag 3.015 A; 2: Au....Au 3.069 A). Compound 3 consists of unique fourfold interpenetrating diamondoid nets. The diamondoid topology is built of heterocubane {Cu4O4} nodes, which are connected by [Au(CN)2]- rods. The Cu-O distances within the {Cu4O4} node vary between 1.927(2) and 2.679(1) A, showing unsymmetric bridging of the copper atoms. Aurophilic interactions are established between the bridging and terminal [Au(CN)2]- metalloligands, and connect the interpenetrating nets, resulting in infinite chains of gold atoms (the Au...Au distances vary between 3.253 and 3.305 [Angstrom]). Compound 4 exhibits a 3-D network constructed from {Cu2(pa)2]2+ nodes connected by square-planar [Ni(CN)4]2- ions. Compounds 1, 2 and 4 are weakly paramagnetic. The cryomagnetic investigation of reveals a gradual increase, followed by a decrease of the chiMT product, as the temperature is lowered. A superposition of ferro- (J1=+20.8 cm(-1)) and antiferromagnetic (J2=-6.4) interactions within the tetranuclear node was found. Antiferromagnetic interactions are established between the tetranuclear nodes (theta=-2.99 K).

Molecular tectonics: control of packing of hybrid 1-D and 2-D H-bonded molecular networks formed between bisamidinium dication and cyanometallate anions

Upon combining the dicationic bis-amidinium tecton 2 bearing four propyl chains with tetra- and hexa-cyanometallate anions neutral 1- and 2-D hybrid networks were obtained. In the case of [M(CN)4]2− (M = Ni(II), Pd(II) and Pt(II)), the control of the spacing between consecutive 1-D H-bonded networks by the presence of the propyl chains was demonstrated. For [M(CN)6]3− (M = Fe(III), Co(III), Cr(III)), 2-D networks presenting hexagonal channels have been obtained. In marked contrast with the case based on the use of 1 for which channels are filled with water molecules, in the case of 2, as expected, the solvent molecules were replaced by propyl chains.

Molecular tectonics: generation of 1- and 2-D copper coordination networks by positional isomeric tectons based on a phenylenediamine backbone bearing two isonicotinoyl moieties

The combination of three isomeric organic tectons 1–3 based on 1,2-, 1,3- and 1,4-phenylenediamine backbones bearing two isonicotinoyl groups with a Cu(OAc)2 neutral complex leads to the formation of 1-D and 2-D coordination networks. Whereas for both tectons 1 and 2 the network is generated through the interconnection of the organic moieties by copper dimers of the paddle-wheel type, in the case of 3, the 2-D network is formed by another type of connector, a binuclear copper complex for which the two metal centres adopt an octahedral coordination geometry.

Molecular tectonics: control of the dimensionality in tetramercaptothiacalixarenes based coordination networks.

Combinations of tetramercaptotetrathiacalix[4]arene pyridyl-appended positional isomers with HgCl2 lead to the formation of neutral coordination networks with their dimensionality imposed by the position of the N atom on the pyridyl group.