Intercalation of ferrocenylalkylammonium cations into the layered lattice of VOPO4

Abstract

Some ferrocenylalkylammonium iodides, [FeII(C5H5){C5H4(CH2)nNR2R′}]+I–(n= 1 or 2; R,R′= H or Me), benzyldimethyl- and benzyltrimethyl-ammonium iodides reacted with VvOPO4·H2O·EtOH suspended in ethanol to afford intercalation compounds of VOPO4·H2O with 0.45[FeII(C5H5)(C5H4CH2NHMe2)]+, 0.20[FeII(C5H5)(C5H4CH2 NMe3)]+, 0.43[FeII(C5H5)(C5H4CH2 CH2NH3)]+, 0.17[FeIII-(C5H5)(C5H4 CH2CH2NMe3)]2+, 0.54PhCH2NHMe2+ and 0.45PhCH2NMe3+. Ferrocenylalkylammonium chlorides, [FeII(C5H5)(C5H4CH2 NHMe2)]+Cl– and [FeII(C5H5)(C5H4CH2 CH2NH3)]+ Cl–, were also intercalated to give compounds of VOPO4·H2O with 0.29[FeIII(C5H5)(C5H4 CH2NHMe2+Cl–)]+ and 0.18[FeIII(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, [FeIII(C5H5)(C5H4CH2 NHMe2+Cl–)]+ and [FeIII(C5H5)(C5H4CH2 CH2NH3+Cl–)]+, in the interlayer space, producing VOPO4–interlayer spacings of 9.8–21.0 A. 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.