Abstract
Charge transport and electronic properties of 4-nitro-4 '-amino-azobenzene compounds with donor-acceptor backbone were examined at the molecular level. Optical properties of all the studied six azobenzene dyes were also explored at the solid-state bulk level, i.e., dielectric constants, conductivity, refractive index, and extinction coefficient values. The introduction of benzyl group enhances whereas propanenitrile diminishes the values for real and imaginary dielectric functions. Moreover, the substitution of 3-methoxy-3-oxopropyl and propanenitrile at amino group decreases the real conductivity values; however, bis(3-methoxy-3-oxopropyl) improves these values. These 4-nitro-4 '-amino-azobenzene compounds showed good refractive indices in the energy range 0-2 eV which revealed that these dyes would be efficient to generate healthier outputs with lower energy inputs. The effect of substituents was also investigated on transfer integrals, frontier molecular orbitals (FMOs), reorganization energies, electron affinity (EA), and ionization energy (IE). The ground-state geometries were optimized by density functional theory at B3LYP/6-31G** level to probe the molecular level properties. The same level of theory was used for the cation and anion optimizations. The hole and electron transfer nature of azo dyes was investigated by evaluating the electron/hole transfer integrals (V-electron/V-hole) as well as hole and electron reorganization energy values. The results exposed that superior V-hole values of Azo2 and Azo4 might lead to these dyes as p-type contenders. Moreover, larger V-electron values of Azo1, Azo3, Azo5, and Azo6 might lead to these dyes as n-type competitors. These results revealed that inspected Azo dyes would be able to serve as competent hole and electron transfer materials within versatile organic semiconductors.