The properties of one-photon absorption (OPA), emission and two-photon absorption (TPA) of a di-2-picolylaminebased zinc ion sensor are investigated by employing the density functional theory in combination with response functions. The responsive mechanism is explored. It is found that the calculated OPA and TPA properties are quite consistent with experimental data. Because the intra-molecular charge transfer (ICT) increases upon zinc ion binding, the TPA intensity is enhanced dramatically. According to the model sensor, we design a series of zinc ion probes which differ by conjugation center, acceptor and donor moieties. The properties of OPA, emission and TPA of the designed molecules are calculated at the same computational level. Our results demonstrate that the OPA and emission wavelengths of the designed probes have large red-shifts after zinc ions have been bound. Comparing with the model sensor, the TPA intensities of the designed probes are enhanced significantly and the absorption positions are red-shifted to longer wavelength range. Furthermore, the TPA intensity can be improved greatly upon zinc ion binding due to the increased ICT mechanism. These compounds are potential excellent candidates for two-photon fluorescent zinc ion probes.

One-photon absorption and two-photon absorption (TPA) properties of three tris(picolyl)amine-based zinc ion sensors are investigated by employing the density functional response theory in combination with the polarizable continuum model. The different isomer and coordination geometry of each probe are taken into account. Special emphasis is placed on the effects of isomerism and the coordination mode on the optical properties. The intra-molecular charge transfer (ICT) properties are specified by natural bond orbital charge analysis. It is shown that the isomerism has non-negligible effects on TPA properties of free ligands. It is found that both the TPA wavelength and the cross section are highly dependent on the coordination mode. When the zinc ion connects with the picolyl unit in the middle of a ligand, the zinc complex has a large TPA intensity in a long wavelength range due to the increased ICT mechanism.

The two-photon absorption (TPA) properties of a new tetraphenylethene derivative and its covalent dimers have been calculated employing the density functional response theory. It is found that linear arrangement of branches can give rise to a cooperative TPA behavior. Partial planarity and linear arrangement are the possible reasons for the observed aggregation-induced TPA enhancement. On the basis of the model molecule, we have designed a series of tetraphenylethene derivatives which differ by donor moieties, connection modes, or central bridges after taking the structure-property relationship of TPA mechanism into account. The TPA spectra of the designed molecules have been calculated, and their TPA properties are analyzed at length. Our results suggest that the change of the connection mode of the carbazole group and the introduction of a vinylene or ethynylene linkage into a molecule can enhance TPA intensity greatly. It can be expected that all of the designed molecules could possess high TPA features. This research is helpful for the design of efficient TPA materials.

No abstract