Fluorescence Lifetimes and Quantum Yields of Rhodamine Derivatives: New Insights from Theory and Experiment

Abstract

Although lifetimes and quantum yields of widely used fluorophores are often largely characterized, a systematic approach providing a rationale of their photophysical behavior on a quantitative basis is still a challenging goal. Here we combine methods rooted in the time-dependent density functional theory and fluorescence lifetime imaging microscopy to accurately determine and analyze fluorescence signatures (lifetime, quantum yield, and band peaks) of several commonly used rhodamine and pyronin dyes. We show that the radiative lifetime of rhodamines can be correlated to the charge transfer from the phenyl toward the xanthene moiety occurring upon the S(0) ← S(1) de-excitation, and to the xanthene/phenyl relative orientation assumed in the S(1) minimum structure, which in turn is variable upon the amino and the phenyl substituents. These findings encourage the synergy of experiment and theory as unique tool to design finely tuned fluorescent probes, such those conceived for modern optical sensors.

Multispectral Phloem-Mobile Probes: Properties and Applications

“…f Savarese et al, 2012. properties of phloem-recalcitrant compounds. It remains to be shown if the glucoside-based probes that we examined here are transported by the recently described SWEET transporters (Chen, 2014).…”

Long-lived and largely red-shifted photoluminescence of solid-state rhodamine dyes: Molecular exciton coupling and structural effect

“…The absorption and fluorescence properties of molecular rhodamines in water and organic solvents have been extensively studied [7][8][9][10][11][12][13][14][15][16][17][18]. However, no such reports on rhodamine solids were found in literature.…”

“…The fluorescence properties of rhodamines are mostly reported in liquid-phases, in which a rhodamine molecule is isolated by surrounding water or organic solvent molecules. Such studies have been the subject of many investigations over last 50 years [7][8][9][10][11][12][13][14][15][16][17][18]. Only recently literature on gas-phase rhodamine fluorescence became available [19][20][21][22][23][24].…”

Prospects of optical refrigeration in oxyfluoride glasses and glass-ceramics: experiments

“…The spectra for all the samples, for pumping at the surface, as well as at a depth of 1-mm from the collection surface, are shown in Figure 1 below. 10 15 concentration (mol %) 20 The mean fluorescence wavelength λ f of the samples is calculated from the photoluminescence (PL) data at a 1 mm depth on the sample, where it is pumped for the calorimetric measurements. For comparison the PL is also made at the sample surface, and the results are shown in Figure 2.…”

“…Also, the intrinsic radiative lifetime can be estimated by extrapolating the data to the very low concentrations. Thus, from the data and fit shown in Figure 4 we calculated the quantum efficiency of the samples as η e = τ measured / τ rad [20], and the results are presented in Table 2. As observed from the measurements with the integrating sphere, the samples with higher quantum efficiency are the doped at a concentration of 2 mol.…”