RESUMEN
Porphyrins are prime candidates for a host of molecular electronics applications. Understanding the electronic structure and the role of anchoring groups on porphyrins is a prerequisite for researchers to comprehend their role in molecular devices at the molecular junction interface. Here, we use the density functional theory approach to investigate the influence of anchoring groups on Ni and Zn diphenylporphyrin molecules. The changes in geometry, electronic structure, and electronic descriptors were evaluated. There are minimal changes observed in geometry when changing the metal from Ni to Zn and the anchoring group. However, we find that the distribution of electron density changes when changing the anchoring group in the highest occupied and lowest unoccupied molecular orbitals. This has a direct effect on electronic descriptors such as global hardness, softness, and electrophilicity. Additionally, the optical spectra of both Ni and Zn diphenylporphyrin molecules exhibit either blue or red shifts when changing the anchoring group. These results indicate the importance of the anchoring group on the electronic structure and optical properties of porphyrin molecules.
RESUMEN
Replacing hydroxyl anions OH¯ by fluorine anions F¯ in borates can cause the blue shift of the UV cutoff edge and also exhibits apparent differences in nonlinear optical (NLO) properties. To clarify the intrinsic difference between OH¯ anions and F¯ anions, several typical borates with different types of cations (p-cations with lone-pair electrons, trivalent rare-earth, and alkaline earth metals) have been studied. The theoretical studies reveal that the blue shift in the band gap of borates with fluorine as compared to those with hydroxyl can be assumed to be the result of weaker interaction of the cation-fluoride (La/Bi/B-F) bonds compared to that of the cation-oxygen and hydroxyl bonds. NLO properties are found to have the order of BiB2O4F > BiB2O4(OH)> LaB2O4F ≈ LaB2O4(OH). The large difference can be attributed mainly to the stereochemical activity of the lone pair (SCALP) effect of the Bi cations and the special BO3F with strong anisotropy as compared to the BO4 group. The energy spanning of F-2p orbitals is more extended in BiB2O4F as compared to LaB2O4F, Sr3B6O11F2, and Ba3B6O11F2 due to the bonding of Bi/B-F, which indicates F-2p orbitals have more chance to overlap with surrounding atoms and enhance the polarizability in all systems. Moreover, the degree of SCALP of the Bi cations is apparently activated by the introduction of the F¯ anions, which causes an obvious enhancement in NLO properties in bismuth borates with F¯. These investigations will help us to classify the solid-state chemistry of F¯ and OH¯ anions in borate systems with different types of metal cations.
