Dimerization and Isomerism Effects on Two-Photon Absorption of Tetraphenylethene Derivatives and Molecular Design for Two-Photon Absorption Materials

Abstract

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.

Responsive mechanism and molecular design of di-2-picolylamine-based two-photon fluorescent probes for zinc ions

“…Our previous work has shown that the B3LYP functional calculations can give reasonable TPA properties which are consistent with the trend of experimental observations. [24][25][26][27][28] The use of the pseudo potential basis sets could probably provide better numerical results, but we believe that the overall picture would not change.…”

“…At the same computational level, the optical properties of different compounds can be compared accurately. [24][25][26][27][28] In this work, we choose a di-2-picolylamine (DPA)-based Zn 2+ ion TP probe as a model molecule. It has been reported that this probe undergoes significant increase of the TPA cross section by the Zn 2+ coordination.…”

Isomerism and coordination mode effects on two-photon absorption of tris(picolyl)amine-based fluorescent probes for zinc ions

“…Our previous work has shown that the B3LYP functional calculations can give reasonable TPA properties which are consistent with the trend of experimental observations. [19][20][21][25][26][27][28][29] The use of bigger basis sets could probably provide better numerical results, but we believe that the overall picture would not change.…”

“…Although isomerism is quite a common phenomenon in chemistry, the effects of isomerism on TPA properties of organic molecules have seldom been discussed in the literature. [23,24] In our previous researches, [25][26][27][28][29] we investigated the influences of isomerism on TPA properties for a series of TPA active molecules. For a probe in solution at room temperature, various isomers of free and bound fluorophores are possible and produce specific spectral features.…”

Excellent ratiometric two-photon fluorescent probes for hydrogen sulfide detection based on the fluorescence resonance energy transfer mechanism

“…32,33 In our previous work, 30 we successfully designed a series of ICT-based TP fluorescent Zn 2+ sensors through using several electron donors and acceptors to increase both TPA and fluorescence quantum yield. Apart from electron donors and acceptors, isomerism also plays an important role in TPA [34][35][36][37] and fluorescence. 38,39 It is well known that the fluorescence quantum yield (0.13) of phenanthrene is lower than that (0.30) of anthracene.…”