Aryl-Substituted Unsymmetrical Benzothiadiazoles: Synthesis, Structure, and Properties

A family of unsymmetrical donor acceptor, ferrocenyl-substituted benzothiadiazoles of types D-1-pi- A-pi-D-2, D-1-pi-A(1)-pi-A(2), D-1-A-pi-D-2, and D-1-A-A(2)-D-2, bearing a variety of electron-donating and electron-withdrawing groups, were designed and synthesized. Their photophysical, electrochemical, and computational properties were explored, which show strong donor acceptor interaction. The presence of electron-rich units anthracene (60 and triphenylamine (6h), and an electron-deficient unit 1,1,4,4tetracyanobuta-1,3-diene (TCBD) (9b) results in lowering of the band gap, which leads to a red shift of the absorption spectrum in these benzothiadiazole systems. The single crystal structures of 6c, 6g, 7a, and 7b are reported, which show marvelous supramolecular interactions.