Design of High-Performance Inorganic–Organic Hybrid Nonlinear Optical Materials Using Superhalogen Al₁₃ and Dianhydrides

Abstract

Novel inorganic−organic hybrid complexes Al 13 −X (X represents the dianhydrides PMDA, NTCDA, and PTCDA) are theoretically designed and studied using density functional theory (DFT) and time-dependent DFT. These conjugated dianhydrides containing four acceptor carbonyl groups are commonly used as electron acceptor materials. These compounds possess large binding energies, reflecting the sufficient binding of Al 13 to the dianhydride molecule. The binding nature of the complexes is of charge transfer type, i.e., electrons are transferred from the aluminum cluster to the dianhydride. All of the aimed complexes have large mean polarizability (α 0 ) and first hyperpolarizability (β 0 ). The β 0 values are explained on the basis of electronic transitions in crucial excited states using the TD-DFT method. Additionally, the hole−electron distribution was analyzed, revealing the nature of electronic excitation. Absorption spectra analysis shows that these complexes have an excellent infrared (IR) transparent region (1000−5000 nm). Therefore, these inorganic−organic hybrid complexes with high stability can be considered as potential candidates for new IR nonlinear optical molecules.