Perylenediimide‐Derived Nonmacrocyclic Host–Guest Donor–Acceptor Assemblies for Long‐Wavelength Emissions and Low‐Threshold Microlasers

Macrocyclic hosts can bind appropriate guests in endo‐cavity or exo‐wall modes to yield Host–Guest cocrystals via weak intermolecular forces. Contrary, it remains challenging to achieve their nonmacrocyclic partners with high‐efficiency fluorescence even lasing due to profound adaptive behaviors during guest inclusion. Here, a variety of low dispersity 1D and 2D assemblies made of a sterically demanding perylenediimide derivative (PDI) host and diverse aromatic guests are realized. Depending on the types and the substituted groups of aromatic guests, these Host–Guest microcrystals show high‐efficiency solid‐state emissions ranging from orange to near‐infrared (NIR). Interestingly, either electron‐deficient or electron‐rich guests can adapt to the cavity of the nonmacrocyclic PDI host in diverse geometries and orientations. Theoretical analysis indicates that the long‐wavelength emissions stem from local or charge‐transfer excited states and the Host–Guest Donor–Acceptor cocrystals are stabilized largely by dispersion forces. The binding of appropriate π‐electron guests makes the PDI‐derived Host–Guest microcrystals function as microscale lasers with low lasing thresholds. The rational creation of these nonmacrocyclic Host–Guest Donor–Acceptor cocrystals offers new insights for developing new crystal structures and high‐efficiency optoelectronic devices. A nonmacrocyclic perylenediimide derivative (PDI) host can bind π‐electron guests with diverse substituted groups and electronic characters into its two cavities to form low dispersity Host–Guest microcrystals with emissions from orange to near‐infrared. Theoretical analysis reveals the cause of the long‐wavelength emissions and dominant dispersion forces of these cocrystals and their lasing properties are even comparable to pure PDI host.