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We demonstrate that one-dimensional photonic crystals with pure nematic liquid-crystal defects can operate as all-optical switching devices based on optical orientational nonlinearities of liquid crystals. We show that such a periodic structure is responsible for a modulated threshold of the optical Fréedericksz transition in the spectral domain, and this leads to all-optical switching and light-induced multistability. This effect has no quasistatics electric field analog, and it results from nonlinear coupling between light and a defect mode.