Polymorphism‐Dependent Emission for Di(p‐methoxylphenyl)dibenzofulvene and Analogues: Optical Waveguide/Amplified Spontaneous Emission Behaviors

The synthesis and optical investigations of di(p‐methoxylphenyl)dibenzofulvene ( 1 ) and its analogues 2 , 3 , 4 , 5 , 6, and 7 with different lengths of alkoxyl chains are presented. All of these molecules exhibit emission in the solid state. The following interesting properties are reported for compound 1 : 1) the solid‐state fluorescence of 1 is dependent on the polymorphism forms; the two crystalline forms 1a and 1b are strongly blue‐ and yellow‐green‐emissive, whereas the amorphous solid is weakly fluorescent with orange emission; 2) on the basis of crystal‐structural analysis, the intermolecular interactions will restrict the internal rotations, leading to fluorescence enhancement for the two crystalline forms 1a and 1b ; however, the difference in emission color between 1a and 1b is ascribed to the molecular conformational alteration; 3) the solid‐state fluorescence of 1 can be tuned by heating and cooling as well as grinding. Importantly, microrods of 1a and 1b exhibit outstanding optical waveguide behaviors. Moreover, amplified spontaneous emission for 1b and multimode‐lasing behavior for 1a are presented. Besides the studies of compound 1 , the crystal structures and solid‐state fluorescence behaviors of 2 , 3 , 4 , 5 , 6, and 7 are also described.