Intercalation of ferrocenylalkylammonium cations into the layered lattice of VOPO4

Abstract

Some ferrocenylalkylammonium iodides, [Fe^II(C₅H₅){C₅H₄(CH₂)_nNR₂R′}]⁺I^–(n= 1 or 2; R,R′= H or Me), benzyldimethyl- and benzyltrimethyl-ammonium iodides reacted with V^vOPO₄·H₂O·EtOH suspended in ethanol to afford intercalation compounds of VOPO₄·H₂O with 0.45[Fe^II(C₅H₅)(C₅H₄CH₂NHMe₂)]⁺, 0.20[Fe^II(C₅H₅)(C₅H₄CH₂ NMe₃)]⁺, 0.43[Fe^II(C₅H₅)(C₅H₄CH₂ CH₂NH₃)]⁺, 0.17[Fe^III-(C₅H₅)(C₅H₄ CH₂CH₂NMe₃)]²⁺, 0.54PhCH₂NHMe₂⁺ and 0.45PhCH₂NMe₃⁺. Ferrocenylalkylammonium chlorides, [Fe^II(C₅H₅)(C₅H₄CH₂ NHMe₂)]⁺Cl^– and [Fe^II(C₅H₅)(C₅H₄CH₂ CH₂NH₃)]⁺ Cl^–, were also intercalated to give compounds of VOPO₄·H₂O with 0.29[Fe^III(C₅H₅)(C₅H₄ CH₂NHMe₂⁺Cl^–)]⁺ and 0.18[Fe^III(C₅H₅)(C₅H₄ CH₂CH₂NH₃⁺Cl^–)]⁺. The intercalation compounds comprise layered VOPO₄ moieties having both the vanadium-(IV) and -(V) states and the ferrocenylalkyl-, benzyldimethyl-, and benzyltrimethyl-ammonium cations as well as ferrocenium-substituted alkylammonium chlorides, [Fe^III(C₅H₅)(C₅H₄CH₂ NHMe₂⁺Cl^–)]⁺ and [Fe^III(C₅H₅)(C₅H₄CH₂ CH₂NH₃⁺Cl^–)]⁺, in the interlayer space, producing VOPO₄–interlayer spacings of 9.8–21.0 Å. The molecular arrangements of these alkylammonium-substituted ferrocene and ferrocenium species in the interlayer space and the electronic states of the guest and host moieties are discussed on the basis of powder X-ray diffraction patterns, and IR, ESR and X-ray photoelectron spectra.