Structural studies on supramolecular adducts of cyclodextrins with the complex [Ru([9]aneS3)(bpy)Cl]Cl

Abstract

a b s t r a c tThe complex [Ru ([9]aneS 3 )(bpy)Cl]Cl (bpy = 2,2 0 -bipyridine) was immobilised in plain b-cyclodextrin (b-CD) and permethylated b-CD (TRIMEB) to yield two adducts with a 1:1 host:guest stoichiometry. The adducts were studied by powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), 13 C{ 1 H} CP/MAS NMR and vibrational spectroscopy (FT-IR and Raman). Results support the formation of stable supramolecular adducts with a proposed geometry in which the coordinated bypiridine fragment of the guest is partially included in the host cavities, and the bulky [9]aneS 3 fragment protrudes out to the interstitial spaces. A packing mode is proposed for [Ru ([9]aneS 3 )(bpy)Cl]Cl Á TRIMEB, obtained by Monte Carlo optimisation of the XRD data. TRIMEB molecules are stacked in tilted channels, with the voluminous part of the guest molecules in the inter-channel space. The behaviour of [Ru ([9]aneS 3 ]) (bpy)Cl]Cl upon CD encapsulation and the chloride ligand hydrolysis process in solution for all compounds were studied in detail by Raman spectroscopy.

Cyclodextrins improve the antimicrobial activity of the chloride salt of Ruthenium(II) chloro-phenanthroline-trithiacyclononane

“…Indeed, the unit cell which best describes the pattern is in the triclinic crystal system with angles close to 90°, but a significant number of reflections were also unaccounted. Preliminary global optimization studies in direct space using FOX (Favre-Nicolin andCerny 2000, 2002) and the pattern collected at ID31 (data not shown) as described by us in a number of previous reports (Pereira et al 2007;Marques et al 2008), led to a structural model of a supramolecular adduct very similar to that found for DIMEBÁCpMo(H 2 biim) (CO) 2 ÁBF 4 ). However, the strongest reflections (appearing at high angle) could not be fully accounted, thus strongly suggesting that most likely a dense material is co-crystallizing.…”

Synthesis and Structural Analysis of Powder Complex of Tris(bipyridine)cobalt(II) Trifluoromethanesulfonate Octahydrate

“…It resulted in very low R factors, leading to 8.85 for GOF. The next application to be on powdered of cobalt complexes containing partially bipy in 2008 [19] with reasonably good fittings resulted in derived Bragg Rfactors of 0.0048-0.0128 and GOF of 1.9-9.75. The powdered oxalate complexes [20] [22], which resulted in the R values of 5.50 (Rp), 9.94 (Rwp) and 2.68 (Rexp) leading to GOF of 13.72, and 0.02 of RBragg.…”

Supramolecular adducts of native and permethylated β-cyclodextrins with (2,2′-dipyridylamine)chlorido(1,4,7-trithiacyclononane)ruthenium(II) chloride: solid-state and biological activity studies

“…For selected bond lengths and angle ranges referring to the Ru 2? coordination sphere please refer to the Table S1 in the Supplementary material Inclusion of the complex [([9]aneS 3 )Ru II (dipa)Cl]Cl (1) into the CDs followed our previously published adaptations of the co-dissolution procedure, based on the relative solubilities of these hosts (Braga et al 2001(Braga et al , 2005Marques et al 2008Marques et al , 2009b. b-CD is hydrophilic, and therefore, it dissolves only in water and not in organic solvents.…”

“…The 260-285 cm -1 spectral region of 1 presents two bands at 271 and 282 cm -1 which can be attributed to RuCl stretching modes by comparison with those of [([9]aneS 3 )Ru II (bpy)Cl]Cl (found at 282 and 298 cm -1 ) (Marques et al 2008). In the same region of the spectra of 2 and 3, bands ascribed to m(Ru-Cl) are also observed, thus confirming that the inclusion procedures did not cause hydrolysis of the guest's ruthenium-coordinated chloride.…”