Computational design of zinc-ion-responsive two-photon fluorescent probes with conjugated multi-structures

A series of conjugated multi-structured fluorescent probe molecules based on a salen ligand were designed and investigated in dimethyl sulfoxide solvent using a quantum-chemical method. The results indicate that the one-photon absorption and fluorescence emission spectra (λO and λEM) of these molecules generally show redshifts (of 23.1–74.5 and 22.7–116.6 nm, respectively) upon the coordination of the molecules to Zn2+. Large Stokes shifts (1511.2–11744.1 cm−1) were found for the molecules, meaning that interference between λO and λEM can be avoided for these molecules. The two-photon absorption spectra of the molecules usually present blueshifts, but the two-photon absorption cross-section (δ) greatly increases (by 221.5–868.0 GM) upon the coordination of the molecules with Zn2+. Most of the molecules show strong two-photon absorption peaks in the range 678.2–824.4 nm, i.e., in the near-infrared region. In a word, the expanded π-conjugated frameworks of these molecules lead to redshifted λO and λEM and enhanced δ values. Moreover, (L-phenyl)​2 and (L-phenyl-ethynyl)2 are the most suitable of the multi-structured molecules examined in this work for use as two-photon fluorescent probes for zinc ion detection in vivo.