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A novel solid-state second harmonic generation (SHG) organic–inorganic hybrid switch [Me3NCH2CH2F]FeBr4 (1) exhibits genuine three-step “on–off–on–off” SHG-switching above-room temperature, which has potential applications in multi-step optical devices.

Graphical abstract: An organic–inorganic hybrid material [Me3NCH2CH2F]FeBr4 exhibits three-step SHG on/off

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