Intercalation of 2-aminoethylferrocene into the layered host lattices MoO3, 2H-TaS2 and α-Zr(HPO4)2·H2O

Abstract

The amino-functionalised ferrocene derivative FcCH₂CH₂NH₂[Fc = Fe(η-C₅H₄)(η-C₅H₄)] has been intercalated under mild conditions into both single-crystal and microcrystalline samples of the layered host lattices MoO₃, 2H-TaS₂, and α-Zr(HPO₄)₂·H₂O. The X-ray powder patterns for the new intercalates have been indexed and yield interlayer lattice expansions of 13.09, 5.89 and 14.54 Å, respectively. The large interlayer expansions of 13.09 and 14.5 Å observed for the intercalates of both MoO₃ and α-Zr(HPO₄)₂·2H₂O suggest the formation of a bilayer of guest molecules within these host lattices. The ⁵⁷Fe Mössbauer spectrum of MoO₃(FcCH₂CH₂NH₂)_0.36 exhibits a quadrupole doublet with an isomer shift δ_Fe= 0.442 mm s^–1 and quadrupole splitting Δ= 2.344 mm s^–1, indicating the presence of unoxidised ferrocene molecules within the oxide layers. Solid-state ¹³C CP-MAS NMR spectra of MoO₃(FcCH₂CH₂NH₂)_0.36 are consistent with the existence of both neutral FcCH₂CH₂NH₂ and FcCH₂CH₂NH₃⁺ moieties within the host. In addition, the changes in the electronic structure of MoO₃ that accompany the interacalation of FcCH₂CH₂NH₂ have been investigated by solid-state photoelectron spectroscopy.