Ultrafast Excited State Intramolecular Proton Transfer Dynamics of 1-Hydroxyanthraquinone in Solution

Ryu, Jaehyun; Kim, Hyun Woo; Kim, Myoung Soo; Joo, Taiha

doi:10.5012/bkcs.2013.34.2.465

Cited by 26 publications

(13 citation statements)

References 30 publications

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“…1 ), including hydroxyl/dihydroxy-anthraquinone (HAQ/DHAQ) and 1-(acylamino)-anthraquinones (AYAAQs) 17 , 18 , 24 – 28 , exhibit the unique ESIPT properties, thus presenting emerging applications in fluorescence probes, dyes and drugs 29 – 33 . The experimental ESIPT evidences have been confirmed for 1-HAQ 34 – 37 , 1,5-DHAQ 37 – 39 , DCAQ and TFAQ 40 – 43 . However, 1,4-DHAQ 37 , 38 and AAAQ 40 – 43 with the similar molecular structures don’t show the ESIPT progress.…”

Section: Introductionmentioning

confidence: 65%

Combined TDDFT and AIM Insights into Photoinduced Excited State Intramolecular Proton Transfer (ESIPT) Mechanism in Hydroxyl- and Amino-Anthraquinone Solution

Zheng

Zhang

Zhao

2017

Sci Rep

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Time-dependent density functional theory (TDDFT) and atoms in molecules (AIM) theory are combined to study the photoinduced excited state intramolecular proton transfer (ESIPT) dynamics for eight anthraquinones (AQs) derivatives in solution. The calculated absorption and emission spectra are consistent with the available experimental data, verifying the suitability of the theory selected. The systems with the excited-state exothermic proton transfer, such as 1-HAQ, 1,5-DHAQ and TFAQ, emit completely from transfer structure (T), while the reactions for those without ESIPT including 1,4-DHAQ and AAAQ appear to be endothermic. Three reaction properties of three systems (1,8-DHAQ, DCAQ and CAAQ) are between the exothermic and endothermic, sensitive to the solvent. Energy scanning shows that 1,4-DHAQ and AAAQ exhibit the higher ESIPT energy barriers compared to 1-HAQ, 1,5-DHAQ and TFAQ with the “barrierless” ESIPT process. The ESIPT process is facilitated by the strengthening of hydrogen bonds in excited state. With AIM theory, it is observed that the change in electrons density ρ(r) and potential energy density V(r) at BCP position between ground state and excited state are crucial factors to quantitatively elucidate the ESIPT.

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Section: Introductionmentioning

confidence: 65%

Combined TDDFT and AIM Insights into Photoinduced Excited State Intramolecular Proton Transfer (ESIPT) Mechanism in Hydroxyl- and Amino-Anthraquinone Solution

Zheng

Zhang

Zhao

2017

Sci Rep

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“…Ryu and S. Sun et al . determined that excited-state intramolecular proton transfer (ESIPT) of 1- hydroxyanthraquinone is less than 50 fs using fluorescence up-conversion by two-photon excitation and femtosecond transient absorption spectroscopy, respectively 20 21 . Ammonium-substituted AQ derivatives have been found to catalyze DNA cleavage upon irradiation with 350 nm light 19 22 23 24 .…”

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confidence: 99%

Ultrafast investigation of photoinduced charge transfer in aminoanthraquinone pharmaceutical product

Zhang

Sun

Zhou

et al. 2017

Sci Rep

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We investigated the mechanism of intramolecular charge transfer and the following radiationless dynamics of the excited states of 1-aminoanthraquinone using steady state and time-resolved absorption spectroscopy combined with quantum chemical calculations. Following photoexcitation with 460 nm, conformational relaxation via twisting of the amino group, charge transfer and the intersystem crossing (ISC) processes have been established to be the major relaxation pathways responsible for the ultrafast nonradiative of the excited S1 state. Intramolecular proton transfer, which could be induced by intramolecular hydrogen bonding is inspected and excluded. Time-dependent density functional theory (TDDFT) calculations reveal the change of the dipole moments of the S0 and S1 states along the twisted coordinate of the amino group, indicating the mechanism of twisted intra-molecular charge transfer (TICT). The timescale of TICT is measured to be 5 ps due to the conformational relaxation and a barrier on the S1 potential surface. The ISC from the S1 state to the triplet manifold is a main deactivation pathway with the decay time of 28 ps. Our results observed here have yield a physically intuitive and complete picture of the photoinduced charge transfer and radiationless dynamics in anthraquinone pharmaceutial products.

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“…TF is a powerful tool to probe excited‐state dynamics of a molecule, such as APTS, that emits from both the reactant and product. In addition, TF provides information on the molecular structure via NWP motions, because amplitudes of NWPs are weighted by the nuclear displacements (Huang‐Rhys factor, HRF) between the two relevant electronic states . For an ultrafast photochemical reaction, NWPs in the product PES may be created by different origins.…”

Section: Introductionmentioning

confidence: 99%

“…In addition, TF provides information on the molecular structure via NWP motions, because amplitudes of NWPs are weighted by the nuclear displacements (Huang-Rhys factor, HRF) between the two relevant electronic states. [11,29] For an ultrafast photochemical reaction, NWPs in the product PES may be created by different origins. For a vibrational mode orthogonal to a reaction coordinate, NWPs launched by the photoexcitation survives the chemical reaction, and its amplitude is proportional to the HRF of the photoexcitation.…”

Section: Introductionmentioning

confidence: 99%

Molecular Dynamics of Excited State Intramolecular Charge Transfer in Solution by Coherent Nuclear Wave Packets

Heo

Joo

2019

ChemPhysChem

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Revealing a proper reaction coordinate in a chemical reaction is the key step towards elucidation of the molecular reaction dynamics. In this report, we investigated the dynamics of intramolecular charge transfer (ICT) of 8‐aminopyrene‐1,3,6‐trisulfonic acid (APTS) occurring in the excited state by time‐resolved fluorescence (TF) and TF spectra. Accurate reaction rates and rate‐dependent nuclear wave packets in the product state allow detailed investigation of the molecular reaction dynamics. The ICT rate is solvent dependent: (34 fs)−1, (87 fs)−1, and (∞)−1 in water, formamide, and dimethylformamide, respectively. By recording spectra of the nuclear wave packets for different reaction rates, chemical species responsible for the emission spectra can be positively identified. The origin of the wave packets can be deduced from the amplitude change of the wave packets at different reaction rates, and the vibrational modes that are associated with the reaction coordinate could be identified. Theoretical calculations of the vibrational reorganization energies reproduce the experimental spectrum of the nuclear wave packets and corroborate the conclusions.

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Ultrafast Excited State Intramolecular Proton Transfer Dynamics of 1-Hydroxyanthraquinone in Solution

Cited by 26 publications

References 30 publications

Combined TDDFT and AIM Insights into Photoinduced Excited State Intramolecular Proton Transfer (ESIPT) Mechanism in Hydroxyl- and Amino-Anthraquinone Solution

Combined TDDFT and AIM Insights into Photoinduced Excited State Intramolecular Proton Transfer (ESIPT) Mechanism in Hydroxyl- and Amino-Anthraquinone Solution

Ultrafast investigation of photoinduced charge transfer in aminoanthraquinone pharmaceutical product

Molecular Dynamics of Excited State Intramolecular Charge Transfer in Solution by Coherent Nuclear Wave Packets

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