| Popis: |
The isotopically labelled amino-functionalised ferrocene derivatives FcCH2CH215NH2 and Fc′CH2CH2NH2[Fc = Fe(η-C5H5)(η-C5H4); Fc′= Fe(η-C5D5)(η-C5D4)] have been synthesized. Their hydrochloride salts and the lamellar intercalation compounds MoO3(Fc′CH2CH215NH2)0.36, and Zr(HPO4)2(Fc′CH2CH215NH2)0.5(H2O)x(x= 0.1–0.5), have been studied by 2H, 15N and, in the last case, 31P solid-state NMR spectroscopy. 2H NMR lineshape analysis has probed aspects of molecular dynamical behaviour. The 2H NMR studies are consistent with rapid reorientation of the η-C5D5 ring about the Fe-ring centroid axis. The deuterons of the η-C5D4CH2CH2NH2 moiety appear to be static on the 2H NMR timescale. Increased averaging of the lineshapes at higher temperatures is interpreted in terms of a rapid wobbling motion of the molecular pseudo-fivefold axis with near axial symmetry, and of progressively increasing amplitude with increase in temperature. Additionally, in the case of the hydrochloride salt and the MoO3 intercalate, but not the Zr(HPO4)2H2O intercalate, a vibration of the molecule in a plane perpendicular to the ferrocene molecular axis, in a manner whereby the molecules are ‘anchored’ at the substituent, is suggested.The 15N CP/MAS NMR spectra reveal features of the host–guest bonding. The spectra of the intercalates are significantly different from those for FcCH2CH215NH2 and [FcCH2CH215NH3]+Cl–. For MoO3(FcCH2CH215NH2)0.36 the 15N NMR shows two distinct environments for 15N within the layers. The major resonance is apparently intermediate between that for [FcCH2CH215NH3]+Cl– and FcCH2CH215NH2, whilst the other minor resonance has been tentatively assigned to a species resulting from oxidation of the guest molecules during the intercalation reaction. The 15N and 31P CP/MAS NMR spectra of Zr(HPO4)2(FcCH2CH2l5NH2)0.5(H2O)x(x= 0.1–0.5) support the hypothesis that the amine is interacting with the acidic layers through P-O ⋯ H-N hydrogen bonds. |
