Two complexes [Ru(Hbiim) 3 ] (1) and [Co(Hbiim) 3 ]$3H 2 O (2) (H 2 biim ¼ 2,2 0 -biimidazole) were synthesized quantitatively and rapidly via a ''liquid-assisted'' solid-state reaction approach. The reaction occurs within minutes of grinding together [Ru(H 2 biim) 3 ](PF 6 ) 2 or [Co(H 2 biim) 3 ]Cl 2 and NH 4 OAc with a few drops of H 2 O 2 as an oxidant and solvent, concomitant with colour changes. The structures of the compounds obtained from the solid-state reaction were confirmed by comparison of their PXRD patterns with simulations based on their single crystal structures. Complex 1 is a 3-fold interpenetrating three-dimensional hydrogen bonded polycatenate network based on a (6,3) net, complex 2 is a double-layer network linked by the lattice water molecules and the Hbiim ligands via hydrogen bonds. For comparison with the solid-state reaction, control reactions were also carried out in solution. Complex 1 was also afforded from the solution reaction. However, a new phase [Co(Hbiim) 3 ]$0.5EtOH (3) was obtained from solution, rather than 2, although it also crystallized from an identical solution of EtOH-water. Complex 3 is a 4-fold interpenetrating three-dimensional hydrogen bonded polycatenate network based on a (10,3)-b net. Interesting, the [M(H 2 biim) 3 ] 2+ (M ¼ Ru and Co) species can be oxidized to the corresponding [M(Hbiim) 3 ] species by oxygen in the presence of acetate anions, which play a determined role in the redox reaction. The deprotonation of the [M(H 2 biim) 3 ] 2+ species triggered by the acetate anions greatly increases the electron density at the M(II) center and shifts the oxidation potentials of M(II) complex to a less positive value. This may provide an effective approach for the generation of high status metal complexes via supramolecular interactions.
A (10,3)-b framework is constructed by the reaction of [Ru(H 2-Biim) 3 ](PF 6 ) 2 and trimesic acid in a ratio of 1 : 1, in which the (10,3)-b net exhibits a two-fold interpenetration featuring 1D nanosized channels. An unprecedented water nanotube consisting of the fused (H 2 O) 28 with a double crown fashion, anchors in the channel.
We describe the first observation of the quantitative and rapid synthesis of a (10,3)-b three-dimensional hydrogen bonded network {[Ru(H 2 biim) 3 ](TMA)} 3 5H 2 O (1 3 H 2 O) (H 2 biim = 2,2 0 -biimidazole; H 3 TMA = trimesic acid) via a "liquidassisted" solid-state reaction approach. The reaction occurs within minutes of grinding together [Ru(H 2 biim) 3 ](PF 6 ) 2 and Na 2 HTMA with a few drops of H 2 O 2 as an oxidant and solvent, concomitant with a color change from yellow (Ru(II) ion) to blue-green (Ru(III) ion). The characterization of the solid-state product was achieved by a combination of a single crystal obtained via seeding and powder diffraction experiments. To compare with the solid-state reaction, similar reactions were also carried out in an EtOH solution. Two complexes {[Ru(H 2 biim) 3 ](TMA)} 3 10H 2 O (2 3 H 2 O) and [Ru(H 2 biim) 3 ](HTMA) (3) were isolated in the presence of a polypyridine base, such as 2,2-dipyridylamine or 2,2 0 :6 0 ,2 00 -terpyridine or 1,10-phenanthroline. Complex 2 is a (6,3) honeycomb two-dimensional hydrogen-bonded network. Complexes 1 and 2 are topological isomers. The formation of multiple robust hydrogen bonds between [Ru(H 2 biim) 3 ] 3þ and TMA may trigger the proton transfer from H 2 biim to TMA, then electron transfer, resulting in Ru(III) status. This may provide an effective approach for the generation of high status metal complexes via supramolecular interactions. Importantly, our experiments suggest that solution crystallization may at times offer more product diversity than grinding.
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