Ultrafast fluorescence study of the effect of carboxylic and carboxylate substituents on the excited state properties of anthracene

Rodríguez-Córdoba, William; Noria-Moreno, Raquel; Navarro, Pedro; Peón, Jörge

doi:10.1016/j.jlumin.2013.08.046

Cited by 9 publications

(9 citation statements)

References 75 publications

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“…As a final example of a probe in this category of reverse polarity sensitivity, anthracene-9-carboxylic acid (A9C) 14 was studied. [61][62][63][64][65] This is a highly complex molecule in aqueous solution, as it not only establishes an acid-base equilibrium, but it has also been shown in the literature that significant dimerization occurs, with the dimer having significantly different fluorescence properties than the monomer. [61][62][63] Photodimerization has also been shown to occur.…”

Section: R a F T Fluorescent Probes Which Exhibit Decreased Emissiomentioning

confidence: 99%

The polarity sensitivity factor of some fluorescent probe molecules used for studying supramolecular systems and other heterogeneous environments

et al. 2018

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Fluorescence spectroscopy provides an excellent technique for investigating heterogeneous systems, due to its high sensitivity and the large effect of the local environment on molecular emission. In addition, the use of polarity-sensitive fluorescent probes as guests in supramolecular host–guest inclusion complexes can be exploited in fluorescent sensors. This paper identifies, tabulates, and quantifies a series of useful polarity-sensitive fluorescent probes, with a wide range of polarity-dependent fluorescence responses. The degree of polarity sensitivity is quantified using the polarity sensitivity factor (PSF), developed in our laboratory. In most cases, such polarity-sensitive probes show increased emission as the local polarity is decreased (PSF > 1); 10 such probes are described. However, less commonly, “reverse polarity dependence” can occur in which probe emission decreases with decreasing polarity (PSF < 1); four such probes are described. The mechanism for the observed polarity-induced fluorescence changes will also be discussed in selected representative cases. The purpose of this paper is to present details on a broad arsenal of polarity-sensitive fluorescence probes with varying properties, with potentially useful applications in the study of heterogeneous systems, including inclusion phenomena, and in practical applications such as fluorescent sensors, which will be useful to researchers studying supramolecular and other heterogeneous systems using fluorescence spectroscopy.

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Section: R a F T Fluorescent Probes Which Exhibit Decreased Emissiomentioning

confidence: 99%

The polarity sensitivity factor of some fluorescent probe molecules used for studying supramolecular systems and other heterogeneous environments

et al. 2018

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“…Comparably, 9-ACA was found to have a dihedral angle of 57º and 88º for the conjugate base, 9-ACA -. 27 This ground-state configuration of 9-ACA is supported by crystallographic data. 42 The non-planar geometry has been attributed to steric interactions between the acid group and the peri-hydrogens on the carbons in the 1 and 8 positions of the anthracene ring.…”

Section: Resultsmentioning

confidence: 55%

“…Previously, a θ of ~33º was calculated by TDDFT for 9-ACA in the excited state, but no ring distortion was reported. 27 The distortion of the anthracene plane observed in 9,10-ADCA but not 9-ACA may be due to greater steric strain on the molecule imposed by the additional carboxylic acid. Puckering of the anthracene ring system upon rotation of the carboxyl groups disrupts the transition dipole moment across the short-axis.…”

Section: Resultsmentioning

confidence: 97%

“…Similar observations have been reported for 9-anthracenecarboxylic acid (9-ACA). 41, 26,27 The structureless emission of 9-ACA was ascribed to enhanced resonance interactions between the carboxylic acid group and the aromatic moiety, due to rotation of the functional group into the plane of the ring system following excitation. 23 DFT calculations of the lowest energy configuration ground-state geometry of 9,10-ADCA reveal a dihedral angle of 57º between the carboxylic acid groups and anthracene plane.…”

Section: Resultsmentioning

confidence: 99%

“…[17][18][19][20] The excited-state behavior of a carboxylic acid functionalized anthracene, 9-anthracenecarboxylic acid (9-ACA) has been the topic of a number of reports. [21][22][23][24][25][26][27] Changes in the emission spectra of 9-ACA have been argued to arise from acid-base equilibrium, solvent and concentration dependent dimerization and formation of higher order aggregates, as well as structural reorganization of the carboxylic acid relative to the anthracene ring in the excited state. 22,24,26 In order to contribute to this discussion, we prepared a series of anthracene derivatives functionalized symmetrically with carboxylic acids; namely 2,6anthracenedicarboxylic acid (2,6-ADCA), 1,4-anthracenedicarboxylic acid (1,4-ADCA), and 9,10-anthracenedicarboxylic acid (9,10-ADCA).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Systematic investigation of the excited-state properties of anthracene-dicarboxylic acids

Rowe

Hay

Maza

et al. 2017

Journal of Photochemistry and Photobiology A: Chemistry

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We report the photophysical properties of three anthracene-dicarboxylic acids -1,4-anthracene dicarboxylic acid (1,4-ADCA), 2,6-anthracene dicarboxylic acid (2,6-ADCA) and 9,10anthracene dicarboxylic acid (9,10-ADCA) -in a series of polar aprotic solvents using steadystate absorption, steady-state emission spectroscopy and time-correlated single photon counting emission lifetime spectroscopy. The addition of carboxylic acid functional groups on the anthracene ring perturbs the electronic transitions oriented along the longitudinal and transverse axes to varying degrees, resulting in differences in the photophysical properties. The three anthracene derivatives exhibit very different excited-state properties in basic solution compared to acidic and neutral solutions. Density functional theory (DFT) calculations reveal that the lowest-energy ground-state structures of both 2,6-ADCA and 1,4-ADCA have dihedral angles between the carboxylic acids and aromatic planes of θ = 0°. DFT calculations also indicate that there is a lower barrier for carboxyl group rotation for 1,4-ADCA (5.5 kcal/mol) than for 2,6-ADCA (8 kcal/mol) in the ground state. For 9,10-ADCA, the same dihedral angle increases to θ = 56.6°. Time-dependent DFT calculations suggest that the carboxyl groups of 1,4-ADCA and 2,6-ADCA remain coplanar with the anthracene ring system in the excited state. In contrast, the calculations reveal significant changes between the ground and excited geometries for 9,10-ADCA as the dihedrals decrease from 56.6º to 27.7° in the first excited state and puckering of the anthracene moiety of 9,10-ADCA is observed.

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Engineering Sensitized Photon Upconversion Efficiency via Nanocrystal Wavefunction and Molecular Geometry

Lai

Jiang

et al. 2020

Angewandte Chemie

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Triplet energy transfer from inorganic nanocrystals to molecular acceptors has attracted strong attention for high‐efficiency photon upconversion. Here we study this problem using CsPbBr3 and CdSe nanocrystals as triplet donors and carboxylated anthracene isomers as acceptors. We find that the position of the carboxyl anchoring group on the molecule dictates the donor‐acceptor coupling to be either through‐bond or through‐space, while the relative strength of the two coupling pathways is controlled by the wavefunction leakage of nanocrystals that can be quantitatively tuned by nanocrystal sizes or shell thicknesses. By simultaneously engineering molecular geometry and nanocrystal wavefunction, energy transfer and photon upconversion efficiencies of a nanocrystal/molecule system can be improved by orders of magnitude.

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Ultrafast fluorescence study of the effect of carboxylic and carboxylate substituents on the excited state properties of anthracene

Cited by 9 publications

References 75 publications

The polarity sensitivity factor of some fluorescent probe molecules used for studying supramolecular systems and other heterogeneous environments

The polarity sensitivity factor of some fluorescent probe molecules used for studying supramolecular systems and other heterogeneous environments

Systematic investigation of the excited-state properties of anthracene-dicarboxylic acids

Engineering Sensitized Photon Upconversion Efficiency via Nanocrystal Wavefunction and Molecular Geometry

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