Controlling the transmission of thin films with external stimuli is an important goal in functional optical materials and devices. Tuning is especially challenging where both broad band (neutral density filtering) and spectrally varied (colour) transmission are required. The external control provided by photochemically driven switching, between transmission levels and colours, is functionally simple from a device perspective. The limits due to the spectral ranges of individual photochromic compounds can be overcome by combining several photochromes within one material or device. Here we show that a combination of photochromic molecular switches immobilised in a PMMA polymer matrix enables tuning of colour and transparency. We show that only a single excitation wavelength is required through the use of the primary inner filter effect and the layered construction of the films in which the photochromes nitrospiropyran (NSP), and nitrothiospiropyran (TSP) or 1,2-bis-terthienyl-hexafluorocyclopentene (DTE) are separated spatially. The approach taken circumvents the need to match photochemical quantum yields and thermal reactivity of the component photochromes. The photochemical switching of the films was characterised by UV/vis absorption spectroscopy and shows that switching rates and photostationary states are limited by inner filter effects rather than the intrinsic properties of photochromes, such as photochemical quantum yields and thermal stability. The photochemical behaviour and stability of the photochromes in solution and in the PMMA films were compared and the concentration range over which self-inhibition of photochemical switching occurs was established. The rate of photochemical switching and the difference in transmission between the spiropyran and merocyanine forms in solution enable prediction of the performance in the films and enable rational design of colour tuning ranges and responsivity in thin film filters.
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