Theoretical study on excited-state intermolecular proton transfer reactions of 1H-pyrrolo[3,2-h]quinoline with water and methanol

Kungwan, Nawee; Daengngern, Rathawat; Piansawan, Tammarat; Hannongbua, Supa; Barbatti, Mario

doi:10.1007/s00214-013-1397-x

Cited by 13 publications

(11 citation statements)

References 48 publications

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“…Finally, we examine the solvent-assisted tautomerization of aqueous 1 H -pyrrolo[3,2- h ]quinoline (HPQ) via excited-state proton transfer (ESPT). The ESPT process of HPQ has been studied both experimentally − and theoretically. − Experiments have been performed on gas-phase clusters (HPQ and a few solvent molecules) and HPQ in bulk solvent, while theoretical studies have focused on the small gas-phase clusters. Here, we will apply the DFT-corrected CASCI method to ESPT in aqueous HPQ.…”

Section: Resultsmentioning

confidence: 89%

Improved Complete Active Space Configuration Interaction Energies with a Simple Correction from Density Functional Theory

Pijeau

Hohenstein

2017

J. Chem. Theory Comput.

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Recent algorithmic advances have extended the applicability of complete active space configuration interaction (CASCI) methods to molecular systems with hundreds of atoms. While this enables simulation of photochemical dynamics in the condensed phase, the underlying CASCI method has some well-known problems resulting from a severe neglect of dynamic electron correlation. Vertical excitation energies, vibrational frequencies, and reaction barriers are systematically overestimated; these errors limit the applicability of CASCI. We develop a correction for the CASCI energy using density functional theory (DFT). The DFT correction incorporates the effect of dynamic electron correlation among the core electrons into the CASCI Hamiltonian. We show that the resulting DFT-corrected CASCI approach is applicable in situations where the usual single-reference DFT methods fail, such as the description of systems with biradicaloid electronic structure and conical intersections between ground and excited electronic states. Finally, we apply this DFT-corrected CASCI approach to ultrafast excited-state proton transfer dynamics. Without the DFT correction, CASCI predicts spurious reaction barriers to these processes, and, as a result, a qualitatively correct description of the dynamics is not possible. With the DFT-corrected CASCI method, we demonstrate qualitative and quantitative agreement with both theory and experiment for two model systems for excited-state intramolecular proton transfer. Finally, we apply the DFT-corrected CASCI method to excited-state proton transfer dynamics in a system with more than 150 atoms.

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Section: Resultsmentioning

confidence: 89%

Improved Complete Active Space Configuration Interaction Energies with a Simple Correction from Density Functional Theory

Pijeau

Hohenstein

2017

J. Chem. Theory Comput.

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“…We hope that the complicated scheme of processes responsible for the photochromism in b-thioxoketones can provide a challenge for the rapidly growing area of theoretical description of photoinduced proton/hydrogen transfer phenomena. [55][56][57][58][59][60][61][62][63][64][65]…”

Section: Discussionmentioning

confidence: 99%

Arresting consecutive steps of a photochromic reaction: studies of β-thioxoketones combining laser photolysis with NMR detection

Pietrzak

Dobkowski

Gorski

et al. 2014

Phys. Chem. Chem. Phys.

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Photochromism of monothiodibenzoylmethane has been studied in a number of environments at different temperatures. Direct laser irradiation of a sample located in the NMR magnet allowed in situ monitoring of the phototransformation products, determining their structure, and measuring the kinetics of the back reaction. These observations, along with the data obtained using electronic and vibrational spectroscopies for rare gas matrix-isolated samples, glasses, polymers, and solutions, as well as the results of quantum-chemical calculations, provide insight into the stepwise mechanism of the photochromism in β-thioxoketones. At low temperature in rigid matrices the electronic excitation leads to the formation of the -SH exorotamer of the (Z)-enethiol tautomer. In solutions, further steps are possible, producing a mixture of two other non-chelated enethiol forms. Photoconversion efficiency strongly depends on the excitation wavelength. Analysis of the mechanisms of the photochromic processes indicates a state-specific precursor: chelated thione-enol form in the excited S2(ππ*) electronic state. The results show the potential of using laser photolysis coupled with NMR detection for the identification of phototransformation products.

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“…[17,36] We suppose that the main fluorescence mechanism for amine 6 in isopropanol changes from ICT to excited state intermolecular proton transfer (ESPT) (Scheme 2). Thus, ESPT with the formation of quinoid-type emissive excited states was studied for different heterocyclic systems [37][38][39][40] and a competition between ICT and ESPT for heterocyclic D-π-A molecular architecture has been reported recently [41].…”

Section: Photophysical Properties Of Cinnoline-based Azide-amine Pairmentioning

confidence: 99%

4-Azidocinnoline—Cinnoline-4-amine Pair as a New Fluorogenic and Fluorochromic Environment-Sensitive Probe

et al. 2021

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A new type of fluorogenic and fluorochromic probe based on the reduction of weakly fluorescent 4-azido-6-(4-cyanophenyl)cinnoline to the corresponding fluorescent cinnoline-4-amine was developed. We found that the fluorescence of 6-(4-cyanophenyl)cinnoline-4-amine is strongly affected by the nature of the solvent. The fluorogenic effect for the amine was detected in polar solvents with the strongest fluorescence increase in water. The environment-sensitive fluorogenic properties of cinnoline-4-amine in water were explained as a combination of two types of fluorescence mechanisms: aggregation-induced emission (AIE) and excited state intermolecular proton transfer (ESPT). The suitability of an azide–amine pair as a fluorogenic probe was tested using a HepG2 hepatic cancer cell line with detection by fluorescent microscopy, flow cytometry, and HPLC analysis of cells lysates. The results obtained confirm the possibility of the transformation of the azide to amine in cells and the potential applicability of the discovered fluorogenic and fluorochromic probe for different analytical and biological applications in aqueous medium.

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Theoretical study on excited-state intermolecular proton transfer reactions of 1H-pyrrolo[3,2-h]quinoline with water and methanol

Cited by 13 publications

References 48 publications

Improved Complete Active Space Configuration Interaction Energies with a Simple Correction from Density Functional Theory

Improved Complete Active Space Configuration Interaction Energies with a Simple Correction from Density Functional Theory

Arresting consecutive steps of a photochromic reaction: studies of β-thioxoketones combining laser photolysis with NMR detection

4-Azidocinnoline—Cinnoline-4-amine Pair as a New Fluorogenic and Fluorochromic Environment-Sensitive Probe

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