Crystal Structures and Fluorescence Spectroscopic Properties of a Series of α,ω-Di(4-pyridyl)polyenes: Effect of...

Crystal structures and fluorescence spectroscopic properties were investigated for a series of all-(E) α,ω-di(4-pyridyl)polyenes (1-5) with different number of double bonds (n). Molecules 1 and 2 (n=1, 2) in crystals are arranged to form partially π-overlapped structures, whereas those of 3-5 (n=3-5) are stacked in a herringbone fashion. All these molecules, the shorter polyenes in particular, are almost nonfluorescent in solution. In the solid state, 1 and 2 are highly emissive as pure organic solids [fluorescence quantum yields (φ_f )=0.3-0.5], while 3 and 4 are only weakly fluorescent (φ_f <0.05). The strongly n-dependent fluorescence properties can be attributed to the largely different molecular arrangements in the crystals. Although 5 is nonfluorescent in the solid state, we observe a very clear structure-property relationship in 1-4. Compounds 1 and 2 become much more emissive in the solid state than in solution as a result of the aggregation-induced emission (AIE) effect.