Modular Synthesis of Biphen[n]arenes Directed by Five-Membered Heterocycles.

Modular synthesis of novel biphen[n]arenes (n = 2-4) with customizable heterocycle blocks, functional skeletons, binding sites, and topological structures could be facilely achieved through the rational design and replacement of reaction modules (furan and thiophene), functional modules (substituted benzene, biphenyl, and naphthalene), and linking modules (methylene). These biphen[n]arenes were characterized by NMR, HRMS, and X-ray crystalline diffraction, complemented by DFT calculations. Their photophysical properties were thoroughly studied.

Synthesis and macrocyclization-induced emission enhancement of benzothiadiazole-based macrocycle.

We presented an effective and universal strategy for the improvement of luminophore's solid-state emission, i.e., macrocyclization-induced emission enhancement (MIEE), by linking luminophores through C(sp3) bridges to give a macrocycle. Benzothiadiazole-based macrocycle (BT-LC) has been synthesized by a one-step condensation of the monomer 4,7-bis(2,4-dimethoxyphenyl)-2,1,3-benzothiadiazole (BT-M) with paraformaldehyde, catalyzed by Lewis acid. In comparison with the monomer, macrocycle BT-LC produces much more intense fluorescence in the solid state (ΦPL = 99%) and exhibits better device performance in the application of OLEDs. Single-crystal analysis and theoretical simulations reveal that the monomer can return to the ground state through a minimum energy crossing point (MECPS1/S0), resulting in the decrease of fluorescence efficiency. For the macrocycle, its inherent structural rigidity prohibits this non-radiative relaxation process and promotes the radiative relaxation, therefore emitting intense fluorescence. More significantly, MIEE strategy has good universality that several macrocycles with different luminophores also display emission improvement.