Langmuir-blodgett films of stilbazole complexes of iridium(I) and rhodium(I)

Complexes of 4-alkoxystilbazoles with iridium and rhodium form stable Langmuir layers at the air-water interface even when the alkoxy chain is relatively short (C₅–C₁₂). The surface pressure-area isotherms indicate that condensed molecular monolayers are obtained. The area per molecule of each compound in its monolayer form is typically 0.60 nm², which agrees well with the cross-sectional area of the [Ir(CO)₂CI] or [Rh(CO)₂CI] head group predicated using molecular models. This suggests that the molecules are oriented with the metal moiety close to the water surface and their alkoxystilbazole ‘rod’ protruding from the plane of the water surface. Such floating monolayers have been transferred on to solid substrates such as glass, aluminium (AI₂O₃/AI/Glass) and silicon (SiO₂/Si) at relatively high speed (10 mm min ^?1) to form Y-type LB assemblies. The UV–Visible absorption properties of these materials in solution and LB film form have been studied. LB films of these complexes yield bathochromically shifted spectra relative to the LB film spectrum of the uncomplexed stilbazole. Additionally, these spectra are often broader and hypsochromically shifted relative to their corresponding solution spectra as a result of the close molecular packing within the LB film and the associated dipole–dipole interactions. The electrically polar nature of the molecules described in this paper suggest that they may be suitable candidates for new pyroelectric materials. Thus the pyroelectric coefficient (the rate of change of electric polarisation with respect to temperature) has been measured for a polar multilayer LB film containing an iridium complex. A pyroelectric coefficient of 3.5 μCm^?2K^?1 (at 30 °C) has been measured, which is one of the highest reported valued for an LB film. Additionally, a low dielectric loss of around 0.01 has been found over the frequency range 50 Hz–1 kHz, indicating that such LB films may be usfeul materials for pyroelectric sensors.