Activation and Tuning of Green Fluorescent Protein Chromophore Emission by Alkyl Substituent-Mediated Crystal Packing

O-Alkyl synthetic analogues of the green fluorescent protein chromophore are nonfluorescent in solution but demonstrate a bright emission in the crystalline state. Three-dimensional steady-state and time-resolved emission spectroscopies in the solid state, as well as single-crystal X-ray diffraction, reveal the nature of complex emission in the crystals. A hypsochromic emission shift with an increase of the alkyl size is determined by the monomer-aggregate emission ratio.