Fluorescent Mechanism of a Highly Selective Probe for Copper(II) Detection: A Theoretical Study

A highly selective probe for copper(II) detection based on the dansyl group was theoretically studied by means of (time-dependent) density functional theory. The calculated results indicated that the oscillator strength of the fluorescent process for the probe molecule is considerably large, but the counterpart of its copper(II) complex is nearly zero; therefore, the predicted radiative rate k_r of the probe is several orders of magnitude larger than that of its complex; however, the predicted internal conversion rate k_ic of both the probe and its complex is of the same order of magnitude. In addition, the simulated intersystem crossing rate k_isc of the complex is much greater than that of the probe due to the effect of heavy atom from the copper atom in the complex. Based on the above information, the calculated fluorescence quantum yield of the probe is 0.16% and that of the complex becomes 10^-6%, which implies that the first excited state of the probe is bright state and that of the complex is dark state. For the complex, the hole-electron pair analysis indicates that the process of S₀ → S₁ belongs to metal-to-ligand charge transfer; its density-of-state diagram visually illustrates that the highest occupied molecular orbital (HOMO) contains the ingredient of the s orbital from the copper atom, which decreases the frontier orbital energy level and the overlap integral of HOMO and LUMO.